Tải bản đầy đủ (.pdf) (40 trang)

Biomimetic Based Applications Part 11 doc

Bạn đang xem bản rút gọn của tài liệu. Xem và tải ngay bản đầy đủ của tài liệu tại đây (639.61 KB, 40 trang )

Biomimetic Applications of Metal Systems Supported by Scorpionates

391
()I"*+% ^% 5)5)H1% /4'% /4)-'/4'$M1#31/)/#/'+% SJ$>e>% -6% /4'% '*KJ5'% 7a"(H$-2% '/% "(C=% @ddRA%
a"(H$-2%'/%"(C=%@dddEC%
%
Cu
Cum
BH
NN
NN
NN
Cum
Cum
O
S
Cu
Ph
BH
NN
NN
NN
Ph
Ph
O
O
S
Ph
Cu
Ph
B


H
NN
NN
NN
Ph
Ph
O
O
Ph
Ph
O
(b) (c)
(a)
%
8)IC%kC%!-('H#("$%1/$#H/#$'%-6b%"E%XaB7NK
,#5=!'
E
f
_,#7P7!'.E,
D
a
h
EA%3E%XaB7NK
&4
E
f
_,#7^E%7^%`%
>M4J+$-OJMfM5'/4J(1#(6"*J(MkM5'/4J(3'*K"(+'4J+'EA%HE%XaB7NK
&4=&4
E

f
_,#7^E%7a^%`%>M
4J+$-OJMkM5'/4J(M@=hM3'*K-L#)*-*'EC%
P/4'$% XaB7NK
&4
E
f
_,#
00
%H-5N('O'1%H-*/")*)*I%H4'("/'%N4'*-("/'1%'O4)3)/%"%1)5)("$%
"$$"*I'5'*/% "$-#*+% /4'% H-NN'$% H'*/'$% 7a"(H$-2% '/% "(C=% @dddEC% XaB7NK
&4
E
f
_,#7^E% 2"1%
'('H/$-H4'5)H"((J%-O)+)K'+%/-%^XaB7NK
&4
E
f
_,#7^E`
q
=%24)H4%)1%"%I +%1N'H/$-1H-N)H%5-+'(%-6%
/4'% +)$"+)H"(% ,#700EMN4'*-O-% 5-)'/J% -6% nP"1'
PZ
=% 3')*I% g&j% 1)('*/% "*+% N$'1'*/)*I%
H-5N"$"3('%:)1)3('Mc0j%6'"/#$'1%7<4)//"Q'$%'/%"(C=%@ddDEC%S4'%'('H/$-H4'5)H"(%$':'$1)3)()/J%-6%
/4'% N4'*-O-rN4'*-OJ% $"+)H"(% $'+-O% N$-H'11=%*-/%-31'$:'+%)*%/4'%"6-$'5'*/)-*'+%
XaB7NK
,#5=!'
E

f
_,#7P7!'.E,
D
a
h
E% 5-+'(=% N$-3"3(J% )5N()'1% H-*1'$:"/)-*% -6% /4'% 1L#"$'%
NJ$"5)+"(%I'-5'/$J%"(1-%)*%/4'%-O)+)1'+%6-$5%^XaB7NK
&4
E
f
_,#7^E`
q
=%':'*%/4-#I4%/4'$'%)1%*-%
1/$#H/#$"(% ':)+'*H'% /-% 1#NN-$/% /4)1% 4JN-/4'1)1C% 0*/'$'1/)*I(J=% 3J% )*/$-+#H)*I% 3#(QJ%
1#31/)/#'*/1%1#H4%"1%tM3#/J(%I$-#N%)*%/4'%para N-1)/)-*%-6%/4'%N4'*-()H%H-M()I"*+=%"%+'H$'"1'%
)*%/4'%Q)*'/)H%1/"3)()/J%-6%/4'%'('H/$-H4'5)H"((J%I'*'$"/'+%+)$"+)H"(%,#700EMN4'*-O-%1N'H)'1%)1%
-31'$:'+% 7.J(:'1/$'% '/% "(C=% >??kEC% S4'% 4'/'$-1H-$N)-*"/'% ()I"*+% 7>M4J+$-OJMfM/M3#/J(M
5'/4J(N4'*J(E3)17f=kM+)5'/4J(NJ$"K-(J(E5'/4"*'% 7^@PE% I":'% /4'% /'$*"$J% H-5N('O%
X,#7^@PE7PFHE_%24'$'%/4'%"H'/"/'%)-*%)1%3-#*+%/-%/4'%5'/"(%2)/4%3-/4%-OJI'*%"/-51C%0/%4"1%
3''*%N$-N-1'+%/4"/%/4'%c
>
P%+-*-$%1'/%N$-:)+'+%3J%^@P%()I"*+%1'$:'1%"1%"%5)5)H%6-$%/2-%
4)1/)*'%"*+%/4'%/J$-1)*'%$'1)+#'1%7<"$/4'*%;%,"$$"*-=%>??fEC%
,-NN'$% "5)*'% -O)+"1'1% 7,#FP"1'1E% H"/"(JK'% /4'% "'$-3)H% -O)+"/)-*% -6%N$)5"$J% "5)*'1% /-%
"(+'4J+'1%)*%1-5'%3"H/'$)"=%J'"1/1=%N("*/1%"*+%5"55"(1%7p()*5"*=%@ddDA%!#$'%'/%"(C=%>??>EC%
S4'% H"/"(J/)H% 1)/'% H-*/")*1% "%S>% H-NN'$% H'*/'$=% X,#7a)1E
f
7Pa
>
E

*
_
qr>q
%7*%`%?%-$%>E=%"*+%/4'%
-$I"*)H%H-6"H/-$%>M7@M"5)*-M@MH"$3-OJ'/4J(EMkM4J+$-OJM@=hM3'*K-L#)*-*'%7S&sEC%,#FP"1'1%
2'$'%H$J1/"(()K'+%)*%/2-%6-$51=%S&sM-*%7&"$1-*1%'/%"(C=%@ddkE%"*+%S&sM-66%7^)%'/%"(C=%@ddeE%
'O4)3)/)*I%/4'%S&s%H-6"H/-$%3-#*+%/-%/4'%5'/"(%-$%fMk%t%+)1/"*/%6$-5%)/=%$'1N'H/):'(JC%S4'%
H-5N('O%XaB7NK
&4=&4
E
f
_,#7^E%7a^%`%>M4J+$-OJMkM5'/4J(M@=hM3'*K-L#)*-*'=%8)IC%kHE%78-1/'$%'/%
"(C=%>???E%2"1%1J*/4'1)K'+%"*+%'('H/$-H4'5)H"((J%H4"$"H/'$)K'+%)*%-$+'$%/-%5-+'(%,#rS&s%
)*/'$"H/)-*1%)*%,#FP"1'1C%0*%/4'%1/$#H/#$'%-6%XaB7NK
&4=&4
E
f
_,#7^E=%H-NN'$%"+-N/1%"%+)1/-$/'+%
1L#"$'MNJ$"5)+"(% I'-5'/$J=% 2)/4% "% (-*I'$% ,#Mc% )*/'$"H/)-*% )*% "O)"(% N-1)/)-*=% "1% 2"1%
N$':)-#1(J% 6-#*+% 6-$% 1)5)("$% H-5N('O'1% 7^)% '/% "(C=% >???E% "*+% )*% S&sM-*% ,#FP"1'1%
7c"Q"5#$"%'/%"(C=%@dd>A%.N')'$%'/%"(C=%@ddhEC%
!-+'(%H-5N('O'1%4":'%3''*%$'N-$/'+%/-%$'N$-+#H'%/4'%N'H#()"$%1/$#H/#$'%"*+%1N'H/$-1H-N)H%
6'"/#$'1% -6% 3(#'% H-NN'$% N$-/')*1% 7p)/"G)5"% '/% "(C=% @dd?A% p)/"G)5"% '/% "(C=% @dd>A% a-(("*+% ;%
S-(5"*=% @dddA% a-(("*+% ;% S-(5"*=% >???A% j"*+"((% '/% "(C=% >???E=% -$% /4'% 6#*H/)-*% -6% /4'1'%
3)-(-I)H"(% '('H/$-*% H"$$)'$1% 7j-$"3"H4'$=% >??hEC% S4'% 5"G-$% 1J*/4'/)H% H4"(('*I'1% /-% J)'(+%
1/$#H/#$"(r1N'H/$-1H-N)H% 5-+'(1% 4":'% 3''*b% @E% -3/")*% ,#700EM/4)-("/'% 1N'H)'1=% 2)/4-#/% /4'%
Biomimetic Based Applications

392
H-*H-5)/"*/% 6-$5"/)-*% -6% +)1#(6)+'1% "*+% ,#70E% 7!"*+"(% '/% "(C=% @ddeE=% "*+% >E% N$-:)+'%

H-5N('O'1%'O4)3)/)*I%+)1/-$/'+% /'/$"4'+$"(%H $+)*"/)-*% -6%,#700E=%24)H4% 5-1/(J% N$'6'$1%"%
/'/$"I-*"(%'*:)$-*5'*/C%.#31/)/#/'+%/$)17NJ$"K-(J(E3-$"/'%()I"*+1%2'$'%-$)I)*"((J%'5N(-J'+%
)*%-$+'$%/-%6#(6)(%/4'1'%$'L#)$'5'*/1%7p)/"G)5"%;%S-(5"*=%@ddkE=%1)*H'%/4'J%"$'%/'/$"4'+$"(%
'*6-$H'$1%"*+%6#$*)14%'*-#I4%'('H/$-*%+'*1)/J%/-%H-NN'$%/-%+)16":-$%-O)+"/)-*%-6%/4)-("/'%H-M
()I"*+1% 7B$#H'% ;%P1/"K'21Q)=% @defA%,4#$H4)((% '/%"(C=% @dekEC% !-$'-:'$=%1/'$)H% 4)*+$"*H'%-*%
XaB7NK
j=jU
E
f
_
M
%N$':'*/1%7"E%/4'%6-$5"/)-*%-6%XaB7NK
j=jU
E
f
_
>
,#% H-5N('O'1% "*+% 73E% /4'%
-HH#$$'*H'%-6%+)$'H/%,#700EM/4)-("/'M,#700E%3$)+I'1=%24)H4%5"J%3'%)*:-(:'+%)*%/4'%5'H4"*)15%
-6%+)1#(6)+'%6-$5"/)-*%7^"NN)*%;%!HF#('J=%@deREC%%
S4'% H-5N('O'1% XaB7NK
!'=!'
E
f
_,-
00
7.jE% 7.j% `% p-*)/$-3'*K'*'/4)-("/'% -$% PM'/4J(HJ1/')*"/'E=%
24)H4% "$'% 1/"3('% )*% 1-(#/)-*% -*(J% "/% (-2% /'5N'$"/#$'1=% $'N$'1'*/% /4'% 6)$1/% 1N'H/$-1H-N)H%
5-+'(1%-6%/4'%,-700EM1#31/)/#/'+%3(#'% ,-NN'$%N$-/')*1%"H/):'%1)/'%7S4-5N1-*% '/%"(C=%@dedEC%
,#700E%H-5N('O'1%2)/4%c=cU=.7.jUE%H $+)*"/)-*%5-/)6=%"1%H-55-*(J%6-#*+%)*%S@%1)/'1=%2'$'%

)1-("/'+% 3J% #1)*I% /4'% c=cU=.M+-*-$% 1H-$N)-*"/'% ()I"*+% Xa7.&4
pM!'
EB7NK
!'=!'
E
>
_
M
%)*1/'"+%-6%
XaB7NK
!'=!'
E
f
_
M
%7S4-5N1-*%'/%"(C=%@dR?EC%S4'%H-5N('O'1%'O4)3)/%1)5)("$%1N'H/$-1H-N)H%6'"/#$'1%
/-% /4'%"6-$'5'*/)-*'+% XaB7NK
!'=!'
E
f
_,#7.jE%1N'H)'1C% F*%)*H$'"1'% )*%/4'% 1/'$)H%3#(Q% -6%/4'%
1H-$N)-*"/'% 1#31/)/#'*/1% 7iMN$-NJ(% I$-#N1% )*% N("H'% -6% 5'/4J(% I$-#N1E% "((-2'+% 6-$% /4'%
H$J1/"(()K"/)-*% -6% "% 5-+'(% -6% "*% -O)+)K'+%S@%1)/'%)*%/4'%6-$5%-6%/4'%H-5N('O%
XaB7NK
)&$=)&$
E
f
_,#7.jE%7.j%`%.,
D
8

k
=%8)IC%D"E%7p)/"G)5"%'/%"(C=%@dd>EC%
S4'% XaB7NK
)&$=)&$
E
f
_,#7.jE% H-5N('O'1% 7.j% `% .,
D
8
k
=% .,!'
f
=% .,&4
f
=% .M/B#E% "$'% I +%
1N'H/$-1H-N)H%5-+'(1%6-$%/4'%-O)+)K'+%S@%1)/'1%7p)/"G)5"%'/%"(C=%@dd?A%p)/"G)5"%'/%"(C=%@dd>A%s)#%
'/%"(C=%@ddhEC%.N'H/$-1H-N)H%5'"1#$'5'*/1%"*+%i8S%H"(H#("/)-*1%-*%XaB7NK
)&$=)&$
E
f
_,#7.,&4
f
E%
4":'%('+%/-%/4'%6-((-2)*I%-31'$:"/)-*1%7j"*+"((%'/%"(C=%>???Eb%@E%/4'$'%)1%"%1/$-*I'$%"*+%5-$'%
H-:"('*/% /4)-("/'M,#% +-*-$% )*/'$"H/)-*% )*% XaB7NK
)&$=)&$
E
f
_,#7.,&4
f

E% /4"*% )*% /4'% S@% 1)/'% -6%
N("1/-HJ"*)*A%>E%/4'$'%)1%"%2'"Q'$%()I"*+%6)'(+%)*%/4'%5-+'(=%H-*1)1/'*/%2)/4%"%5-$'%$'I#("$%
/'/$"4'+$"(% I'-5'/$J% "$-#*+% /4'% 5'/"(A% fE% "*% )*H$'"1'% )*% /4'% '66'H/):'% *#H('"$% H4"$I'% -6%
H-NN'$%6$-5%N("1/-HJ"*)*%/-%XaB7NK
)&$=)&$
E
f
_,#7.,&4
f
E=%24)H4%)5N()'1%"%2'"Q'$%+-*-$%1'/%)*%
/4'% 5-+'(% 7c=c=c% 6$-5% XaB7NK
)&$=)&$
E
f
_E% $'("/):'% /-% /4'% c7a)1E
>
.7!'/E% +-*-$% 1'/% )*%
N("1/-HJ"*)*C%
%
iPr
iPr
BH
NN
NN
NN
Cu
iPr
iPr
S
iPr

iPr
F
F F
F
F
iPr
Cu
iPr
BH
NN
NN
NN
iPr
iPr
S
N
iPr
iPr
N
(a) (b)
%
8)IC%DC%!-('H#("$%1/$#H/#$'%-6b%"E%XaB7NK
)&$=)&$
E
f
_,#7.,
D
8
k
EA%3E%XaB7NK

)&$=)&$
E
f
_,#7/)5
!'
EC%
F%6#$/4'$%,#700E%H-5N('O%2)/4%/4'%XaB7NK
)&$=)&$
E
f
_
M
%1#NN-$/)*I%()I"*+%2"1%1J*/4'1)K'+=%#1)*I%
"% /4)-O-M)5)+"K-('% 7/)5
!'
E% "1% H-M()I"*+% 7B"1#5"(()HQ% '/% "(C=% >??>EC% S4'% $'1#(/)*I% H-5N('O%
XaB7NK
)&$=)&$
E
f
_,#7/)5
!'
E%'O4)3)/1%"%1L#"$'MNJ$"5)+"(%I'-5'/$J%"$-#*+%/4'%H-NN'$%)-*=%2)/4%
"%c
h
.%+-*-$%1'/%78)IC%D3EC%XaB7NK
)&$=)&$
E
f
_,#7.!'05E%H"*%3'%H-*1)+'$'+%"%1/$#H/#$"(%5-+'(%-6%

1-5'% 5#/"*/% "K#$)*1% 7,"*/'$1% ;% n)("$+)=% @ddfA% i'*% B(""#2'*% ;% ,"*/'$1=% @ddfA% +'*%
B(""#2'*% '/% "(C=% @ddfE% "*+% *)/$-1-HJ"*)*% 7"% $'+% H-NN'$% N$-/')*E% 7<4)//"Q'$% '/% "(C=% >???A%
^)'3'$5"*% '/% "(C=% >??@E=% 3-/4% )*:-(:)*I% "% N'*/"H $+)*"/'+% ,#700E% )-*C% S4'% '66'H/% -6% /4'%
Biomimetic Applications of Metal Systems Supported by Scorpionates

393
)*H$'"1'% -6% /4'% H $+)*"/)-*% *#53'$%2"1%)*:'1/)I"/'+%3J%H-5N"$)*I%/4'%
1/$#H/#$"(r1N'H/$-1H-N)H% N$-N'$/)'1% -6% XaB7NK
)&$=)&$
E
f
_,#7.!'05E% 2)/4% /4-1'% -6%
XaB7NK
)&$=)&$
E
f
_,#7.,&4
f
EC%
S4'%5'/"((-'*KJ5'%H-NN'$%*)/$)/'%$'+#H/"1'%7,#c0jE%N("J1%"%Q'J%$-('%)*%/4'%*)/$-I'*%HJH('%
1)*H'%)/%$'+#H'1%*)/$)/'%)-*1%7cP
>
M
E%/-%*)/$)H%-O)+'%7cPEC%S4'%$'1/)*I%1/"/'%"H/):'%1)/'%-6%,#c0j%
H-*1)1/1%-6%"%,#700E%)-*%/'/$"4'+$"((J%H $+)*"/'+%3J%/4$''%cM+-*-$%4)1/)+)*'1%"*+%"%2"/'$%
5-('H#('%7S>%1)/'E%7n-++'*%'/%"(C=%@dd@EC%S4)1%1)/'%)1%H-**'H/'+%/-%"%S@%'('H/$-*%/$"*16'$%1)/'%3J%
"% a)1M,J1% 3$)+I'C% F% 6)$1/% 4JN-/4'1)1% -6% /4'% '*KJ5'U1% H"/"(J/)H% 5'H4"*)15=% N$-N-1'+% 3J%
F:'$)((% 7a#(1'% '/% "(C=% @dRdA% F:'$)((=% @ddDE=% H-*/'5N("/'1% /4'% )*)/)"(% $'+#H/)-*% -6% /4'% 5'/"(%
H'*/'$%72)/4%'('H/$-*1%14#//('+%6$-5%/4'%S@%1)/'E%"*+%1#31'L#'*/%3)*+)*I%-6%*)/$)/'%/-%,#70E%
3J% 5'"*1% -6% /4'% c% "/-5% 7K

@
Mc% H $+)*"/)-*EC% S4)1%
K
@
Mc% H $+)*"/)-*% )1% 1#NN-$/'+% 3J%
'ON'$)5'*/"(%':)+'*H'%-*%5-+'(%H-5N('O'1%7a"(6'*%;%S-(5"*=%@ddhA%!"4"N"/$"%'/%"(C=%@ddDEC%
.#31'L#'*/%N$-/-*"/)-*%-6%/4'%1#31/$"/'%2-#(+%I):'%2"/'$%"*+%"%H-NN'$M*)/$-1J(%H-5N('O=%
N$'1#5"3(J% "*% #*1/"3('% Y,#cP]
@?
%1N'H)'1%7g*'5"$Q%;%8'(/4"5=%@dehE=%24'$')*%cP%)1%
$'"1-*"3(J% H-*1)+'$'+% /-% 3'% K
@
Mc% '*+M-*% H $+)*"/'+% /-% /4'% 5'/"(C% S4'% H-NN'$M*)/$-1J(%
)*/'$5'+)"/'% )1% H$#H)"(% 6-$% /4'% H"/"(J/)H% 5'H4"*)15% -6% ,#c0j=% "*+% 6-$% /4)1% $'"1-*% 1-5'%
5-*-*#H('"$%,#McP%H-5N('O'1%2'$'%N$'N"$'+%/-%5-+'(%/4)1%1N'H)'1C%,-NN'$%H-5N('O'1%"1%
5-+'(1% 6-$% *)/$)/'% $'+#H/"1'% 2'$'% 'O"5)*'+% )*% $'6C% 7<"11'$% '/% "(C=% >??>EC% S4'% H-5N('O%
XaB7NK
/B#
E
f
_,#7cPE% )1% /4'% 6)$1/% 1/$#H/#$"((J% H4"$"H/'$)K'+% 5-*-*#H('"$% H-NN'$M*)/$-1J(%
H-5N('O%78)IC%e"E%7,"$$)'$%'/%"(C=%@dd>A%j#II)'$-%'/%"(C=%@ddfEC%
%
tBu
BH
NN
NN
N
N
Cu

tBu
tBu
N
O
tB u
BH
NN
N
N
N
N
Cu
tBu
tBu
O
O
N
(a)
(b)
%
8)IC%eC%!-('H#("$%1/$#H/#$'%-6b%"E%XaB7NK
/B#
E
f
_,#7cPEA%3E%XaB7NK
/B#
E
f
_,#7cP
>

EC%
S4'% 5'/"(% N$'1'*/1% "% N1'#+-/'/$"4'+$"(% I'-5'/$J% "*+% "% K
@
Mc% '*+M-*% cP% H $+)*"/)-*=%
1#NN-$/)*I% )*+)$'H/(J% /4'% K
@
McP% '*+M-*% 4JN-/4'1)1% 6-$% /4'% Y,#cP]
@?
%1N'H)'1%-6%,#c0jC%
c)/$)H% -O)+'% 3)*+)*I% )1%$':'$1)3('=% 1)*H'% )/%)1% (-1/%#N-*% "NN()H"/)-*%-6% "% :"H##5%-$% 24'*%
N#$I)*I% 2)/4% "$I-*C% S2-% -/4'$% ,#M*)/$-1J(% H-5N('O'1% 2)/4% 1H-$N)-*"/'1% "1% 1#NN-$/)*I%
()I"*+1=%*"5'(J%XaB7NK
/B#=)&$
E
f
_,#7cPE%"*+%Xa,7NK
/B#=)&$
E
f
_,#7cPE=%4":'%3''*%H4"$"H/'$)K'+%
)*% /4'% 1-()+% 1/"/'% 78#G)1"2"% '/% "(C=% >??REC% B-/4%/4'1'%1N'H)'1%"$'%1/$#H/#$"(%"*"(-I#'1%-6%
XaB7NK
/B#
E
f
_,#7cPE=% 'O4)3)/)*I%/'/$"4'+$"(% H $+)*"/)-*%-6% /4'%5'/"(=% 2)/4%"% K
@
Mc% '*+M-*%
cPC% .N'H/$-1H-N)H% ':)+'*H'% "*+% ab initio%H"(H#("/)-*1%4":'%$':'"('+%/4"/%"((%/4'%/4$''%
H-5N('O'1%4":'%"%Y,#cP]

@@
%'('H/$-*)H%1/$#H/#$'=%3'//'$%+'1H$)3'+%2)/4%"%,#70EMcP
.
%$"+)H"(%
)*/'$"H/)-*% H4"$"H/'$)K'+% 3J% "% 1)I*)6)H"*/% H-:"('*HJC% S4'% 1/'$)H"((J% 4)*+'$'+% 1H-$N)-*"/'%
()I"*+%XaB7NK
/B#
E
f
_
M
=%"1%2'((%"1%3')*I%"%N1'#+-/'/$"4'+$"(%'*6-$H'$=%4"1%/4'%)5N-$/"*/%$-('%-6%
1/"3)()K)*I%cP%H $+)*"/)-*=%3J%N$-/'H/)*I%)/%6$-5%N-11)3('%+)1N$-N-$/)-*"/)-*%)*/-%c
>
P%"*+%
cP
>
M
C%F%1)5)("$%cP%+'H-5N-1)/)-*%N"/42"J%-HH#$1%':'*%)*%/4'%'*KJ5'=%#*+'$%H-*+)/)-*1%-6%
4)I4% cP% H-*H'*/$"/)-*% 7u"HQ1-*% '/% "(C=% @dd@EC% cP% +)15#/"/)-*% )*% 5-+'(% H-5N('O'1% )1%
1/$-*I(J%)*6(#'*H'+%3J%/4'%*"/#$'%-6%/4'%1#31/)/#'*/1%j%"*+%jU%-*%/4'%XaB7NK
j=jU
E
f
_
M
%()I"*+C%
0*/'$'1/)*I=% *-/% -*(J% 1/'$)H% 3#(Q% 7'CIC=% /B#% I$-#NE=% 3#/% "(1-% /4'% '('H/$-*% 2)/4+$"2)*I%
Biomimetic Based Applications


394
H4"$"H/'$% 7'CIC,%,8
f
%I$-#NE%-6%/4'%XaB7NK
j=jU
E
f
_M1#31/)/#'*/1% /'*+1% /-%1(-2% /4'% $"/'% -6% cP%
+)1N$-N-$/)-*"/)-*C% !'H4"*)1/)H% )*:'1/)I"/)-*1%1#II'1/%/4"/%/4'%N$-H'11%-HH#$1%3J%"*%
'('H/$-N4)()H%"//"HQ%-6%"%1'H-*+%cP%5-('H#('%-*%/4'%)*)/)"(%,#McP%"++#H/=%/4#1%J)'(+)*I%"%
XaB7NK
j=jU
E
f
_,#7cPE
>
%"++#H/C%8-((-2)*I%cMc%H-#N()*I%"*+%PM"/-5%/$"*16'$=%c
>
P% "*+%
,#700EM7cP
>
M
E%"$'%I'*'$"/'+C%%
S4'% ,#700EM*)/$)/-%6-$5% -6%,#c0j=%24)H4%'O4)3)/1%K
>
MP=PU%H $+)*"/)-*% -6% cP
>
M
% /-%H-NN'$%
7!#$N4J%'/%"(C=%@ddeA%l'1'(-:%'/%"(C=%@ddRE=%)1%1/"3)()K'+%3J%4J+$-I'*%3-*+%)*/'$"H/)-*1%2)/4%

/4'% N$-/')*M5"/$)O% 1)+'% H4")*1C% F% 6'2% ,#700EM*)/$)/-% 5-+'(% H-5N('O'1% 2)/4%
4J+$-/$)17NJ$"K-(J(E3-$"/'%H-M()I"*+1%4":'%3''*%1/$#H/#$"((J%H4"$"H/'$)K'+=%14-2)*I%')/4'$%"%
1J55'/$)H%-$%"1J55'/$)H%K
>
MP=P%H $+)*"/)-*%5-+'%-6%cP
>
M
=%+'N'*+)*I%-*%/4'%NJ$"K-(J(%
1#31/)/#'*/1C% B#(QJ% j%1#31/)/#'*/1=% 1#H4% "1% tM3#/J(% I$-#N1=% 6":-$% "*%"1J55'/$)H% "$$"J% "1%
6-#*+%)*%/4'%"H/):'%1)/'%-6%,#c0jC%S4)1%)1%-31'$:'+%)*%/4'%H-5N('O'1%XaB7NK
/B#
E
f
_,#7cP
>
E%
78)IC% e3E% 7S-(5"*=% @dd@E% "*+% XaB7NK
/B#=)&$
E
f
_,#7cP
>
E% 7^'4*'$/% '/% "(C=% >??eE=% 24'$'"1%
XaB7NK
)&$=)&$
E
f
_,#7cP
>
E% 7^'4*'$/% '/% "(C=% >??eE=% XaB7NK

,8f=!'
E
f
_,#7cP
>
E% "*+%
XaB7NK
!'=!'
E
f
_,#7cP
>
E% 7.H4*')+'$% '/% "(C=% @ddRE% 14-2%"%1J55'/$)H%3)+'*/"/'%*)/$)/'%
H $+)*"/)-*C%<4'*%#1)*I%"%*'#/$"(%/$)17NJ$"K-(J(E5'/4"*'%"1%"%H-M()I"*+=%/2-%cP
>
M
%)-*1%"$'%
H $+)*"/'+%/-%,#700Eb%-*'%*)/$)/'%)1%K
@
MP%"*+%/4'%1'H-*+%-*'%)1%K
@
Mc%3-#*+%7^'4*'$/%'/%"(C=%
>??eEC%
j'H'*/(J%)/%4"1%3''*%+)1H-:'$'+%/4"/%/4'%*)/$)/'%)-*%)1%3-#*+%)*%"%/$)+'*/"/'%6"14)-*%)*%/4'%
$'+#H'+%6-$5%-6%,#c0j=%2)/4%)/1%-OJI'*%"/-51%H $+)*"/'+%/-%,#70E%"*+%"*%"++)/)-*"(%2'"Q%
,#Mc% )*/'$"H/)-*% 7F*/-*J#Q% '/% "(C=% >??kEC% S4)1% 3)*+)*I% 5-+'% 2-#(+% "((-2% 5)*)5"(%
1/$#H/#$"(% $'"$$"*I'5'*/1% 3'/2''*% /4'% $'"H/)*I% K
>
MP=PU% cP
>

M
%"*+%/4'%)*H)N)'*/%1)+'M-*%
H $+)*"/'+%cP%7Y,#cP]
@?
%1N'H)'1EC%S4'%1N'H/$-1H-N)H%N$-N'$/)'1%-6%/4'%5-+'(%H-5N('O'1%
XaB7NK
/B#=)&$
E
f
_,#7cPE% "*+% Xa,7NK
/B#=)&$
E
f
_,#7cPE=% )*% 24)H4% cP% )1% '*+M-*% 3-#*+% /-% /4'%
5'/"(=% 2'$'% H-5N"$'+% /-% /4-1'% -6% ,#c0j% 7v1-:% '/% "(C=% >??DEC% S4)1% 4"1% "((-2'+% 6-$% /4'%
+'/'$5)*"/)-*%-6%/4'%3)*+)*I%5-+'%-6%/4'%Y,#cP]
@@
%1N'H)'1%)*%N$-/')*%1-(#/)-*1%"1%1/$-*I(J%
3'*/%'*+M-*%3#/%*-/%1)+'M-*%78#G)1"2"%'/%"(C=%>??REC%
,-5N$'4'*1):'% $':)'21% +'1H$)3)*I% 1/$#H/#$"(% "*+% 6#*H/)-*"(% "1N'H/1% -6% H-NN'$% +)-OJI'*%
5-+'(1%4":'%3''*%$'N-$/'+%7p)/"G)5"%;%!-$-M-Q"=%@ddhA%^'2)1%;%S-(5"*=%>??hA%!)$)H"%'/%"(C=%
>??hEC%S4'%'5N(-J5'*/%-6%1H-$N)-*"/'%()I"*+1%)*%H-NN'$%3)-5'/)H1%7p)/"G)5"=%@dd>A%p)/"G)5"%
;%S-(5"*=% @ddkA%n'**"$)%;% !"$H4)w=%>??dE% "*+%/-%#*+'$1/"*+%H-NN'$%N$-/')*%"H/):'M1)/'1%
H4'5)1/$J%7S-(5"*=%>??DE%2"1%$':)'2'+%)*%/4'%N"1/C%%
3.2 Zinc biomimetic systems
\)*H%)1%'11'*/)"(%/-%"((%6-$51%-6%()6'%"*+%)/%)1%N$-3"3(J%/4'%5-1/%3)-M$'(':"*/%5'/"(C%a#5"*%
3')*I1%H-*/")*%"*%":'$"I'%-6%"NN$-O)5"/'(J%>%/-%f%I%-6%K)*H%"*+%)/%4"1%3''*%6-#*+%/4"/%fx%-6%
/4'%4#5"*%I'*-5'%H-*/")*%/4'%H-+'%6-$%K)*H%6)*I'$%N$-/')*1%7p(#I=%@dddEC%S4'$'%"$'%"3-#/%
h??%/4$''M+)5'*1)-*"(%1/$#H/#$'1%6-$%K)*H%N$-/')*1=%$'N$'1'*/)*I%"((%1)O%6#*+"5'*/"(%'*KJ5'%
H("11'1b% -O)+-$'+#H/"1'1% 7"(H-4-(% +'4J+$-I'*"1'% 6"5)(JE=% /$"*16'$"1'1=% 4J+$-("1'1%

7H"$3-OJN'N/)+"1'% 6"5)(JE=% (J"1'1% 7H"$3-*)H% "*4J+$"1'% 6"5)(JE=% )1-5'$"1'1=% "*+% ()I"1'1%
7F#(+=% >??DEC% S4#1=% K)*H% )1% )*:-(:'+% )*% "% 2)+'% :"$)'/J% -6% 5'/"3-()H% N$-H'11'1% )*H(#+)*I%
H"$3-4J+$"/'=%()N)+=%N$-/')*=%"*+%*#H(')H%"H)+%1J*/4'1)1%"*+%+'I$"+"/)-*C%!-*-*#H('"$%K)*H%
'*KJ5'1%2'$'% H#$$'*/(J%1/#+)'+%3J%1':'$"(%3)-)*-$I"*)H%$'1'"$H4%I$-#N1%2)/4%3)-5)5'/)H%
H-5N('O'1C%j'H'*/%"*+%1#31/"*/)"(%$':)'21%3J%nC%&"$Q)*%7&"$Q)*=%>???A%&"$Q)*=%>??hA%&"$Q)*=%
>??eE=% aC% l"4$'*Q"5N% 7l"4$'*Q"5N=% >??eE% "*+% cC% B#$K("66% 78)1H4'$% '/% "(C=% >??dE H-:'$%
"(5-1/%"((%"1N'H/1%-6%1J*/4'/)H%K)*H%'*KJ5'%"*"(-I#'1C%S4#1=%4'$'%2'%2)((%1#55"$)1'%1-5'%
"1N'H/1%-6%1J*/4'/)H%"*"(-I#'1%-6%K)*H%'*KJ5'1%/4"/%6'"/#$'%1H-$N)-*"/'%()I"*+1C%
Biomimetic Applications of Metal Systems Supported by Scorpionates

395
S4'% 5-('H#("$% H4"$"H/'$)K"/)-*% -6% K)*H% 1)/'1% )*% 3)-(-I)H"(% 1J1/'51% H"5'% 6)$1/% /4$-#I4%
$'N("H)*I%/4'%1N'H/$-1H-N)H"((J%1)('*/%K)*H%2)/4%/4'%H4$-5-N4-$)H%5'/"(%H-3"(/C%0*%N"$/)H#("$=%
,-700E%1#31/)/#/)-*%4"1%3''*%2)+'(J%'5N(-J'+%"1%"%/ (%6-$%H-*:'$1)-*%-6%1N'H/$-1H-N)H"((J%
1)('*/% \*700EMH-*/")*)*I% N$-/')*1% )*/-% 1/)((M6#*H/)-*)*I% '*KJ5'1=% 3#/% 6-$% 24)H4% -N/)H"(%
7"31-$N/)-*=%5"I*'/)H%H)$H#("$%+)H4$-)15%7!,iEE%"*+%5"I*'/)H%$'1-*"*H'%7*#H('"$%5"I*'/)H%
$'1-*"*H'% 7c!jE=% '('H/$-*% N"$"5"I*'/)H% $'1-*"*H'% 7g&jE=% '('H/$-*% *#H('"$% +-#3('%
$'1-*"*H'% 7gciPjEE% 1N'H/$-1H-N)H% /'H4*)L#'1% "((% H"*% 3'% N$-+#H/):'(J% "NN()'+% /-%
#*+'$1/"*+%'*KJ5'%1/$#H/#$'%"*+%6#*H/)-*%7!"$'/%;%l"((''=%@ddfA%B'$/)*)%'/%"(C=%>??@EC%j'H'*/%
'O"5N('1% )*:-(:'+% 4)I4M6$'L#'*HJ% "*+% M6)'(+% '('H/$-*% N"$"5"I*'/)H% $'1-*"*H'% 7a8g&jE%
)*:'1/)I"/)-*% -6% H-3"(/M1#31/)/#/'+% K)*H% '*KJ5'1% 7p$KJ1/'Q% '/% "(C=% >?@?E=% g&jrgciPj%
1/#+)'1%-6%"%,-M1#31/)/#/'+%\*%6)*I'$%N$-/')*=%S8%000F%7<"(13J%'/%"(C=%>??fE=%!,i%1/#+)'1%-6%"%
:"$)'/J%-6%,-M1#31/)/#/'+%\*%'*KJ5'1%"*+%5-+'(%H-5N-#*+1%7^"$$"3''%'/%"(C=%@ddeEC%0*%/4'%
N"1/%/4'%1#31/)/#/)-*%-6%K)*H%)*%'*KJ5'1%3J%H"+5)#5%2"1%"(1-%"//'5N/'+=%)*%"*%'66-$/%/-%/"Q'%
"+:"*/"I'% -6%
@@f
,+% c!j% 1N'H/$-1H-NJ% )*% I")*)*I% 1/$#H/#$"(% "*+%5'H4"*)1/)H% )*6-$5"/)-*%
7,-('5"*=% @dd>EC% S4'1'% '66-$/1% 2'$'% "3"*+-*'+% 3'H"#1'% )/% 3'H"5'% / % -3:)-#1% /4"/%
H"+5)#5% "*+% K)*H% 4":'% '11'*/)"((J% *-/4)*I% )*% H-55-*% )*% /'$51% -6% ()I"*+% N$'6'$'*H'1=%
H $+)*"/)-*%*#53'$1%-$%1/"3)()/)'1C%

\)*H%'*KJ5'1%)*%/4'%$'1/)*I%1/"/'%"(5-1/%2)/4-#/%'OH'N/)-*%H-*/")*%K)*HM3-#*+%2"/'$%7l"((''%
;%F#(+=%@ddfEC%S4'%/'/$"4'+$"(%XYZ[\]\*MPa
*
_%K)*H%H'*/$'%)1%/4'%5-1/%H-55-*%1/$#H/#$"(%
6'"/#$'% 6-#*+%6-$% /4'% "H/):'%1)/'% -6% K)*H% '*KJ5'1C% 0*%/4'1'% '*KJ5'1%K)*H% )1% 3-#*+%/-% /4'%
N$-/')*% 3J% /4$''% "5)*-% "H)+% $'1)+#'1C% S4'% K)*H% 3)*+)*I% $'1)+#'1% Z=% [% "*+% \% "$'% ')/4'$%
4)1/)+)*'=%I(#/"5"/'=%"1N"$/"/'%-$%HJ1/')*'C%%
%
(His)N N(His )
Zn
N(His)
OH
2
(His)N
O(Glu/Asp)
Zn
N(His)
OH
2
(His)N
S( Cys)
Zn
N(His)
OH
2
(His)N
S(Cys)
Zn
S( Cys)
OH

2
(Cys)S S(Cys )
Zn
S( Cys)
OH
2
(Cy s)S S(Cy s)
Zn
S( Cys)
S(Cys)
(a)
(b) (c)
(d) (e) (f )
%
8)IC%RC%, $+)*"/)-*%5-/)61%)*%5-*-*#H('"$%K)*H%'*KJ5'1b%"E%H"$3-*)H%"*4J+$"1'=%5"/$)O%
5'/"((-N$-/'"1'1A%3E%/4'$5-(J1)*=%H"$3-OJN'N/)+"1'%FA%HE%N("*/%N'N/)+'%+'6-$5J("1'1%
7&i81EA%+E%"(H-4-(+'4J+$-I'*"1'=%H-3"("5)*'%)*+'N'*+'*/%5'/4)-*)*'%1J*/4"1'A%'E%kM
"5)*-(':#()*"/'%+'4J+$"/"1'A%6E%F+"%icF%$'N")$%N$-/')*C%%
F(5-1/% "((% /$)N('% H-53)*"/)-*1% -6% /4'1'% $'1)+#'1% "$'% 6-#*+% )*% K)*H% '*KJ5'1C% i#$)*I% /4'%
$'1/)*I% 1/"/'=%/4'% 6-#$/4%N-1)/)-*% -6%/4'% XYZ[\]\*MPa
*
_% "H/):'% 1)/'% )1% #1#"((J% -HH#N)'+% 3J%
2"/'$%-$%"%4J+$-O)+-%()I"*+%78)IC%RE%7&"$Q)*=%>??hA%p$""/K%;%!'/K('$Mc-(/'=%>??DEC%0*%5"*J%
H"1'1=%H4"$"H/'$)1/)H"((J% )*%/4'% "(H-4-(+'4J+$-I'*"1'% 7FiaE%"*+% H-3"("5)*'% )*+'N'*+'*/%
5'/4)-*)*'% 1J*/4"1'% 7,F0!.E% I$-#N=% /4'% 2"/'$% 5-('H#('% -*(J% $'N$'1'*/1% /4'% :"H"*/%
H $+)*"/)-*% 1)/'% 24)H4%+#$)*I% H"/"(J1)1% )1% -HH#N)'+% 3J% /4'% 1#31/$"/'C% !-$'% )5N-$/"*/(J=%
/4-#I4=%"*+%'OH(#1):'(J%)*%/4'%H"$3-*)H%"*4J+$"1'%7,FE%"*+%5"/$)O%5'/"((-N$-/'"1'1%7!!&E%
I$-#N=% /4'% 2"/'$% ()I"*+% )1% /4'% 6#*H/)-*"(% $'"I'*/% 24)H4% )1% +'N$-/-*"/'+% /-% 3'H-5'% /4'%
N-2'$6#(%\*yPa%*#H('-N4)('%24)H4%)1%$'1N-*1)3('%6-$%/4'%'66)H)'*HJ%-6%/4'%4J+$-(J/)H%K)*H%
'*KJ5'1C%0*6"H/=%+#$)*I%/4')$%H"/"(J/)H%HJH('%/4'%/'/$"4'+$"(%-$%N1'#+-/'/$"4'+$"(%I'-5'/$)'1%

-6% /4'1'% K)*H% '*KJ5'1% "$'% L#)/'% 6('O)3('% "*+% H4"*I'% 3'/2''*% "% /'/$"MH $+)*"/'+% "*+% "%
N'*/"MH $+)*"/'+% K)*H% H'*/$'C% g1N'H)"((J% /4'% H $+)*"/)-*% -6% "% H"$3-OJ("/'% +-*-$% 'CIC% "%
I(#/"5"/'%H"*%'"1)(J%:"$J%)*%/4'%1-%H"(('+%H"$3-OJ("/'%14)6/%3'/2''*%"%5-*-+'*/"/'%"*+%"%
3)+'*/"/'%H $+)*"/)-*C%S4)1%6('O)3)()/J%)1%/4-#I4/%/-%3'%'11'*/)"(%6-$%/4'%4J+$-(J/)H%"H/):)/J%-6%
5"*J%-6%/4'%K)*H%'*KJ5'1C%
Biomimetic Based Applications

396
B)-)*-$I"*)H% H $+)*"/)-*% H4'5)1/1% 24-% "$'% /$J)*I% /-% 5-+'(% 1#H4% "H/):'% 1)/'1% 3J% 1)5N('%
()I"*+1% "*+% K)*H% H-5N('O'1% "$'% /4'$'6-$'% 6"H)*I% 1':'$"(% N$-3('51b% "E% /4'% 6('O)3)()/J%
5'*/)-*'+%"3-:'%)1%+)66)H#(/%/-%5)5)H%2)/4-#/%"%1#$$-#*+)*I%N$-/')*%N-HQ'/A%3E%"5)*-%"H)+1%
-*%/4')$%-2*%H $+)*"/'%K)*H%)-*%*-/%-*(J%:)"%/4'%"5)*-%"H)+%$'1)+#'%3#/%"(1-%:)"%/4'%cM%-$%
,M/'$5)*#1%-6%/4'%1'L#'*H'A%HE%N$-/'H/'+%"5)*-%"H)+1%-$%15"((%-()I-N'N/)+'1%"$'%-6/'*%*-/%
3#(QJ% '*-#I4% /-% N$':'*/% /4'% 6-$5"/)-*% -6% 3)1()I"*+% H-5N('O'1% -$% 4J+$-O)+-% 3$)+I'+%
+)*#H('"$%K)*H%H-5N('O'1=%/4)1%)1%"(1-%/4'%H"1'%6-$%)5)+"K-('1%-$%/4)-(1=%24)H4%/'*+%/-%6-$5%
-()I-M% -$% N-(JM*#H('"$% H-5N('O'1C% i#$)*I% 1/#+)'1% 3J% H $+)*"/)-*% H4'5)1/1% ")5'+% "/% /4'%
5-+'(()*I% -6% K)*H% '*KJ5'1=% 5"*J% N-(J+'*/"/'% ()I"*+1% 4":'% 3''*% +'1)I*'+% 24)H4% ('":'%
$ 5%6-$%G#1/% -*'%2"/'$%()I"*+% )*%/4'%H $+)*"/)-*%1N4'$'%-6% K)*H%7&"$Q)*=%>??hEC%0*%/4-1'%
H"1'1%24'$'%/4'%"H)+)/)'1%-6%/4'1'%H-5N('O'1%4":'%3''*%+'/'$5)*'+%/4'J%N$-:)+'%':)+'*H'%
6-$% /4'%H $+)*"/)-*% *#53'$rNK
"
%$'("/)-*14)NC%0*%N"$/)H#("$=%^\*7Pa
>
E%H-5N('O'1% 2)/4% ^%
3')*I%"%/'/$"+'*/"/'%()I"*+%4":'%NK
"
%:"(#'1%"/%-$%"3-:'%R%7!"$'L#'Mj):"1%'/%"(C=%>??hEC%B#/=%
5-1/% 1/$)Q)*I(J=% "((% "//'5N/1% /-% N$'N"$'% ^\*7Pa
>
E% H-5N('O'1% 2)/4% /$)N-+"(% 1H-$N)-*"/'1%

()I"*+1% 4":'% $'1#(/'+% )*% /4'% )1-("/)-*% -6% /4')$% +'N$-/-*"/'+% +'$):"/):'1=% /4'% ^\*yPa%
H-5N('O'1C%%
S$)N-+"(%1H-$N)-*"/'%()I"*+1%4":'%3''*%"NN()'+%1#HH'116#((J%)*%K)*H%5-+'(%H-5N('O'1C%S4')$%
Q'J%"+:"*/"I'1% "$'%"%V6"H)"(W% 3)*+)*I%H"#1)*I% /'/$"4'+$"(%/-% -H/"4'+$"(%K)*H%H'*/$'% "*+%"%
$"/4'$%$)I)+%I'-5'/$J%H-5N"$'+%/-%/4'%-6/'*%:'$J%6('O)3('%5"H$-HJH()H%()I"*+1C%F1%8)I#$'%d%
14-21=%/4'J%H"*%6-$5%hM=%kM=%-$%DMH $+)*"/'%K)*H%H-5N('O'1%+'N'*+)*I%-*%/4'%H-#*/'$"*)-*1%
N$'1'*/%7j-53"H4%'/%"(C=%@dddEC%
B"1)*I%-*%3-$+'$()*'%N$-N'$/)'1%-6%K)*H=%5)O'+%4"$+%"*+%1-6/%()I"*+%'*:)$-*5'*/1%5"Q'%6-$%
N'$6'H/(J%1/"3('%H-5N('O'1=%N#$'(J%4"$+%-$%1-6/%()I"*+%'*:)$-*5'*/1%5"Q)*I%K)*H%#*2)(()*I%
/-% "HH'N/%/4'% ()I"*+%/4)-("/'C% S4)1% )1%-*'% -6%/4'%5-1/%)5N-$/"*/%N$-N'$/)'1%I-:'$*)*I%/4'%
3)-(-I)H"(% H4'5)1/$J% -6% K)*H% 7l"4$'*Q"5N=%>??eEC%!-+)6)H"/)-*1%$'I"$+)*I%/4'%1/'$)H"(%
4)*+$"*H'%H"*%'"1)(J%3'%'5N(-J'+%/-%5"*J%1H-$N)-*"/'%()I"*+1%/-%N$':'*/%+)5'$%6-$5"/)-*%
'CIC%3J%"//"H45'*/%-6%3#(QJ%$'1)+#'1%7j%I$-#N1E%/-%/4'%()I"*+1C%0*%$'H'*/%1/#+)'1%6#*H/)-*"(%
I$-#N1%"$'%"//"H4'+%/-%/4'%()I"*+1%/-%5)5)H%/4'%'*KJ5'%N-HQ'/1%5-$'%H(-1'(JC%S4)1%"((-21%
/4'%1/"3)()1"/)-*%-6%H $+)*"/'+%1#31/$"/'1=%2"/'$%-$%4J+$-O)+-%()I"*+1%3J%4J+$-I'*%3$)+I'1C%
.)5)("$%)*/'$"H/)-*1%"$'%6-#*+%)*%'*KJ5'1C%
%
R'
R
BH
NN
NN
NN
Zn
R
R
R
BH
NN
NN

NN
R
R
R'
R'
R'
R'
R'
R'
R
BH
NN
NN
NN
Zn
R
R
X
X
R'
R'
R'
R
BH
NN
NN
NN
Zn
R
R

Y
R'
R'
(a)
(c)
(b)
%
8)IC%dC%&J$"K-(J(3-$"/'%K)*H%H-5N('O'1%2)/4%hM=%kM=%"*+%DMH $+)*"/'+%K)*Hb%"E%2)/4%*-*%
H $+)*"/)*I%"*)-*1A%3E%2)/4%4"$+%H-()I"*+1%ZA%HE%2)/4%1-6/%H-()I"*+1%[C%
!-1/%5-+'(1%6-$%5-*-*#H('"$%K)*H%'*KJ5'1%+'1H$)3'+%1-%6"$%H-*1)1/%-6%/$)N-+%()I"*+1%2)/4%
/4$''% -$% 6-#$% c% +-*-$1% /-% 5)5)H% 5-*-*#H('"$% K)*H% '*KJ5'1% 2)/4% /4$''% K)*H% 3)*+)*I%
4)1/)+)*'% $'1)+#'1%7'CIC% /4'% 5"/$)O%5'/"((-N$-/'"1'1%-$% H"$3-*)H%"*4J+$"1'E% 7&"$Q)*=%>???A%
&"$Q)*=% >??hEC% P6/'*% 1/'$)H"((J% 4)*+'$'+% 4J+$-/$)17NJ$"K-(M@MJ(E3-$"/'% ()I"*+1% "$'% #1'+% /-%
5)5)H% /4)1% /$)174)1/)+)*'E% 5-/)6% 3J% /4$''% NJ$"K-(M@MJ(% +-*-$1C% g1N'H)"((J% /4'% 2-$Q1% -6% aC%
Biomimetic Applications of Metal Systems Supported by Scorpionates

397
l"4$'*Q"5N%"*+%nC%&"$Q)*%4":'%4'(N'+%/-%'(#H)+"/'%1':'$"(%3)-H"/"(J/)H%5'H4"*)151%2)/4%
N-(J7"K-(J(E3-$"/'MK)*H% 5-+'(1C% .H-$N)-*"/'% K)*H% H-5N('O'1% 4":'% 3''*% $'H-I*)1'+% 3J%
:"$)-#1%$'1'"$H4%I$-#N1%"1%:'$1"/)('%/ (1%)*%/4'%L#'1/%6-$%*'2%K)*H%3)*+)*I%I$-#N1%1#)/"3('%
6-$%'*KJ5'%)*4)3)/-$1C%S4'%1J*/4'1)1%-6%1#H4%1/$#H/#$"(%'*KJ5'%7)*4)3)/-$E%5-+'(1%#1#"((J%
1/"$/1%6$-5%/4'%4J+$-O)+-%H-5N('O'1C%%
S4'% 5-1/% +)66)H#(/% /"1Q=% 24)H4% )1% *-/% 6#((J% "H4)':'+% "1% J'/=% )1% /4'% )1-("/)-*% -6% "%
^XaB7NK
j
E
f
_\*7Pa
>
E`

q
%H"/)-*%7j#6%'/%"(C=%@ddDA%B'$IL#)1/%;%&"$Q)*=%@dddE%7XaB7NK
j
E
f
_%+'*-/'1%
"*J% -*'% 1#31/)/#/'+% /$)17NJ$"K-(J(E3-$"/'% ()I"*+E=% /4'% 5")*% $'"1-*% 6-$% 24)H4% )1% /4'%
4J+$-(J/)H%+'1/$#H/)-*% -6%/4'% XaB7NK
j
E
f
_
M
%()I"*+1%)*% "H)+)H%5'+)"C%0*% "((% H"1'1%1/#+)'+=% /4'%
XaB7NK
j
E
f
_\*yPa%H-5N('O'1%"$'%/4'%'"1)'1/%/-%N$'N"$'%7F(16"11'$%'/%"(C=%@ddfA%j#6%'/%"(C=%@ddDA%
j#6%;%l"4$'*Q"5N=%@ddDEC%0*%G#1/%"%6'2%H"1'1%/4'J%H-#(+%3'%)*+#H'+%/-%$'('"1'%2"/'$%"*+%
6-$5%/4'%+)*#H('"$%H-5N('O'1%^XaB7NK
j
E
f
_\*yPay\*XaB7NK
j
E
f
_`
q

%703$"4)5%'/%"(C=%>??DEA%6#((%
+'N$-/-*"/)-*% 2)/4% 6-$5"/)-*% -6% /4'% *'#/$"(% 5-('H#("$% 1N'H)'1% ^XaB7NK
j
E
f
_\*yPy
\*XaB7NK
j
E
f
_`%4":'%3''*%"H4)':'+%)*%-*'%H"1'%7j#6%;%l"4$'*Q"5N=%@ddDEC%%
S4'%XaB7NK
j
E
f
_\*yPa%H-5N('O'1%-2'%/4')$%1/"3)()/J%3-/4%/-%/4'%6"H/%/4"/%/4'%1/'$)H"((J%("+'*%
XaB7NK
j
E
f
_
M
%()I"*+1%'*6-$H'%"%(-2%H $+)*"/)-*%*#53'$%"*+%/4"/%/4'J%H$'"/'%"%4J+$-N4-3)H%
N-HQ'/%"*+%"*%'*H"N1#("/)-*%-6%/4'%\*yPa%#*)/C%0*H$'"1)*I%/4'%N-("$)/J%74"$+*'11E%*'"$%K)*H%
7'CIC%3J%"%NJ$)+J(%1#31/)/#/'+%()I"*+E%"((-21%/4'%H $+)*"/)-*%*#53'$%/-%3'%)*H$'"1'+A%"1%"%
$'1#(/=%-31'$:'+%)*%/4'%'*KJ5'M1#31/$"/'%5-+'(%H-5N('O%XaB7NK
&J=!'
E
f
_\*7Pa

>
EP&P7P&4E
>
%
7<')1%'/%"(C=%@ddRE=%/4'%4J+$-(J/)H%"I'*/%2"/'$%"*+%/4'%-$I"*-N4-1N4"/'%7'5N(-J'+%/-%5-+'(%
/4'%1#31/$"/'E%"$'%"//"H4'+%/-%K)*H%"/%/4'%1"5'%/)5'C%%
S4'% XaB7NK
j
E
f
_\*yPa% H-5N('O'1% 2'$'%14-2*%/-% 3'% "3('% /-% N'$6-$5=% )*% "% 1/-)H4)-5'/$)H%
2"J=%"((%4J+$-(J/)H%$'"H/)-*1%H"/"(JK'+%3J%K)*H%'*KJ5'1%7l"4$'*Q"5N=%@dddA%&"$Q)*=%>??hEC%
B'"$)*I%:-(#5)*-#1%-$I"*)H%1#31/)/#'*/1=%/4'J%1#66'$%6$-5%/2-%()5)/"/)-*1%2)/4%$'1N'H/%/-%
H"/"(J/)H%"H/)-*C%S4'J%"$'%4J+$-N4-3)H%"*+%+-%*-/%+)11-(:'%)*%2"/'$=%/4'$'3J%$'*+'$)*I%/4'%
$'"I'*/%a
>
P%#*":")("3('=%"*+%/4'J% 6-$5%:'$J%1/"3('%H-5N('O'1%2)/4%/4'%H"$3-OJ("/'1%"*+%
N4-1N4"/'1%$'1#(/)*I%6$-5%4J+$-(J1)1C%P*%-*'%4"*+%/4)1%)1%#*6":-#$"3('%"*+%1/)((%$'L#)$'1%
'66-$/1%)*%-$+'$%/-%-:'$H-5'%)/=%3#/%-*%/4'%-/4'$%4"*+%)/%4"1%N$-:)+'+%)5N-$/"*/%H-5N-#*+1%
6-$%/4'%1/$#H/#$'%H-$$'("/)-*%3"1'+%5'H4"*)1/)H%6)*+)*I1C%
S4'%XaB7NK
j=jU
E
f
_\*7PaE%H-5N('O'1%7j%`%/B#=%&4=%,#5=%jU%`%a=%!'=%/B#E%78)IC%@?"E%7F(16"11'$%
'/%"(C=%@dd@A%p)/"G)5"%'/%"(C=%@ddfA%^ *'J%'/%"(C=%@ddfA%j#6%;%l"4$'*Q"5N=%@ddDE=%)*H(#+)*I%
XaB7NK
j
E
f

_
M
%)*H-$N-$"/)*I%4J+$-I'*%3-*+)*I%"HH'N/)*I%'1/'$%1#31/)/#'*/1=%$'"H/%"1%6#*H/)-*"(%
5-+'(1%"HH-$+)*I%/-% /4'%H"$3-*)H%"*4J+$"1'% 5'H4"*)15%7^ *'J%'/%"(C=%@ddfA%j-53"H4% ;%
l"4$'*Q"5N=%>??@A%a"55'1%'/%"(C=%>??>A%B'$IL#)1/%'/%"(C=%>??fA%^)N/-*%'/%"(C=%>??fA%^)N/-*%;%
g(()1=% >??eE% "*+% 6-$5% 3)H"$3-*"/'% 6$-5% ,P
>
C% aJ+$-I'*1#(6)+-=% /4)-("/-=% N4'*-("/-% "*+%
"(H-4-("/-% XaB7NK
j
E
f
_
M
%H-5N('O'1%"$'%"HH'11'+%3J%1#31/)/#/)-*% $'"H/)-*1% 2)/4% a
>
.=% /4)-(1=%
N4'*-(1%-$%"(H-4-(1%7j#6%;%l"4$'*Q"5N=%@ddDA%B'$IL#)1/%'/%"(C=%>???A%B$"*+%'/%"(C=%>??@EC%%
%
R'
R
B
H
NN
N
N
N
N
Zn
R

R
OH
R'
R'
tBu
B
H
NN
N
N
NN
Zn
tBu
tBu
O
O
RO
(a) (b)
%
8)IC%@?C%./$#H/#$'%-6b%"E%4J+$-O)+-%H-5N('O'1%XaB7NK
j=jU
E
f
_\*7PaEA%3E%%
XaB7NK
/B#=!'
E
f
_\*7P,PPjE%"1%"%H"$3-*)H%"*4J+$"1'%5-+'(C%
Biomimetic Based Applications


398
S4'% H-5N('O% ^XaB7NK
&4=!'
E
f
_
>
\*
>
7a
f
P
>
E`,(P
h
% 7&#'$/"%;% ,-4'*=%>??>E% )1%)5N-$/"*/% 6-$%/4'%
$'(':"*H'% -6% )/1% 1/$#H/#$'% )*% /'$51% -6% 4J+$-(J/)H% K)*H% '*KJ5'1=% /4"/% #1'% 4J+$-I'*M3-*+%
1/"3)()K'+%2"/'$%*#H('-N4)('1%/-%N'$6-$5%N'N/)+'%3-*+%H('":"I'C%
<)/4%+)"(QJ(%H"$3-*"/'%/4'%4J+$-O)+-%H-5N('O'1%6-$5%5-*-"(QJ(%H"$3-*"/-%H-5N('O'1%78)IC%
@?3E% 7j#6% '/% "(C=% @ddDA% l"4$'*Q"5N=% @dddEC% S4'1'% "$'% "(1-% "HH'11)3('% 3J% "% $'"H/)-*% -6%
"(H-4-("/-% H-5N('O'1% 2)/4% ,P
>
=% "% $'"H/)-*% /4"/% )1% "*"(-I-#1% /-% /4'% H"$3-*)H% "*4J+$"1'%
H"/"(J1)1C%S4)1% ':'*%"((-21% /4'%H"/"(J/)H% 6-$5"/)-*%-6% +)"(QJ(%H"$3-*"/'% 6$-5%"(H-4-(1% "*+%
,P
>
%#*+'$%N$'11#$'%7l"4$'*Q"5N=%@dddEC%B)*+)*I%1/#+)'1%2)/4%1#(6-*"5)+'%)*4)3)/-$1%4":'%
"(1-%3''*%+'1H$)3'+%7a"$/5"**%;%l"4$'*Q"5N=%@ddhA%B$-53"H4'$%;%l"4$'*Q"5N=%>??hEC
%

S4'% N$-/'H/):'% N-HQ'/% N$-:)+'+% 3J%/4'%NJ$"K-(J(3-$"/'%()I"*+1%XaB7NK
,#5=!'
E
f
_
M
%"*+%
XaB7NK
&4=!'
E
f
_
M
%4"1%5"+'%)/%N-11)3('%/-%-3/")*%1/"3('%"*+%)*'$/%K)*H%H-5N('O'1%XaB7NK
j
E
f
_\*M
3"1'% -6% /4'% "*)-*)H% *#H('-3"1'1% 7)C'C% /4J5)*'=% #$"H)(=% +)4J+$-#$"H)(=% HJ/-1)*'=% "+'*)*'=%
I#"*)*'=% +)"5)*-N#$)*'=%O"*/4)*'=% 4JN-O"*/4)*'E% )*%/4')$% +'N$-/-*"/'+%6-$51%7B"+#$"%;%
l"4$'*Q"5N=%>??>E%"*+%/-%)*:'1/)I"/'%/4'%$'"H/):)/J%-6%"5)*-"H)+1%/-2"$+%K)*H%7j-53"H4%'/%
"(C=%>??>EC%S4'%H-5N('O%XaB7NK
,#5=!'
E
f
_\*7PaE%4"1%3''*%$'N-$/'+%/-%H('":'%"H/):"/'+%"5)+'1%
"*+% '1/'$1% 7j#6% ;% l"4$'*Q"5N=% @ddDEC% P/4'$% 4J+$-O)+-% H-5N('O'1=% 'CIC%
XaB7NK
,#5=!'
E

f
_\*7PaE=% "$'% "3('% /-% 4J+$-(J1'% "5)+'1% 7l"4$'*Q"5N=% @dddA% &"$Q)*=% >??hEC%
S4)1% )*+)H"/'1% /4"/% 1#H4% 5-+'(% H-5N('O'1% "$'% "(1-% 1/$#H/#$"(% "*+% 6#*H/)-*"(% 5-+'(1% 6-$%
5"/$)O%5'/"((-N$-/'"1'1%7!!&1EC%S4'$'6-$'=%5"/$)O%5'/"((-N$-/'"1'1%5-+'(%N$-N'$/)'1%"$'%
"(1-% #/)()1'+% 6-$% 3)*+)*I% 1/#+)'1% 2)/4% N$-/'"1'%)*4)3)/-$1%7j#6%'/%"(C=% @ddDA% l"4$'*Q"5N=%
@dddEC% 0*% /4'1'% 3)*+)*I% 1/#+)'1% /4'% H $+)*"/)-*% N$-N'$/)'1%-6% /4'%K)*H% 3)*+)*I%I$-#N1% -6%
!!&% )*4)3)/-$1% "$'% )*:'1/)I"/'+C% 0*% N"$/)H#("$% /4'% N)-*''$)*I% 2-$Q% -6% ,-4'*% 7&#'$/"% ;%
,-4'*=%>??>A%&#'$/"%;%,-4'*=%>??fA%u"H-31'*%;%,-4'*=%>??hA%&#'$/"%'/%"(C=%>??hA%&#'$/"%'/%"(C=%
>??kA%&#'$/"%'/%"(C=%>??DA%u"H-31'*%'/%"(C=%>??eE%"*+%l"4$'*Q"5N%7j#6%'/%"(C=%@ddDA%S'Q'1/'%;%
l"4$'*Q"5N=%>??DA%S'Q'1/'%;%l"4$'*Q"5N=%>??DE%)*%/4)1%6)'(+%4"1%/-%3'%4)I4()I4/'+C%
%
Ph
B
H
NN
N
N
NN
Zn
Ph
Ph
O
NH
O R
Ph
BH
NN
NN
NN
Zn

Ph
Ph
N
S
O
(a)
(b)
CO
2
Et
BH
NN
NN
NN
Zn
CO
2
Et
H
O
O
O
H
O
O
(c)
%
8)IC%@@C%"E%!-+'(%H-5N('O%6-$%!!&1%2)/4%3-#*+%4J+$-O"5"/'%)*4)3)/-$A%3E%B)+'*/"/'%Q
>
M

H $+)*"/)-*%-6%NJ$)+)*'/4)-*'%)*%3)-5)5'/)H%K)*H%H-5N('O%XaB7NK
&4=!'
E
f
_\*^A%HE%1/$#H/#$'%
-6%XaB7NK
,P>g/=!'
E
f
_\*7a
>
PE7PFHEC%
,-55-*%K)*H%3)*+)*I%I$-#N1%"NN()'+%1#HH'116#((J%)*%N'N/)+"1'%)*4)3)/-$1%4":'%3''*%')/4'$%
"% H"$3-OJ()H% "H)+=% "% 4J+$-O"5)H% "H)+% -$%"%/4)-(%6#*H/)-*"()/JC%j'"H/)-*1%-6%
XaB7NK
j=jU
E
f
_\*7PaE% H-5N('O'1% 2)/4% H"$3-OJ()H% "H)+1=% 4J+$-O"5)H% "H)+1% -$% /4)-(1% J)'(+%
H"$3-OJ("/-=%4J+$-O"5"/-%78)IC%@@"E%"*+%/4)-("/-%H-5N('O'1%7j#6%'/%"(C=%@ddDA%&"$Q)*=%>??hEC%
S4'1'%H-5N('O'1%5"J%3'%#*+'$1/ +%"1%3)-5)5'/)H%H-5N('O'1%/4"/%5-+'(%/4'%H $+)*"/)-*%
'*:)$-*5'*/% -6% /4'1'% K)*H% 3)*+)*I% I$-#N1% 3-#*+% /-% /4'% H"/"(J/)H% K)*H% )-*% )*% /4'% 5"/$)O%
5'/"((-N$-/'"1'1C% ,-4'*% "*+% H-2-$Q'$1% 6)$1/% #/)()K'+% H $+)*"/)-*% H-5N('O'1% /-% 5-+'(%
+$#IMN$-/')*%)*/'$"H/)-*1%-6%)*4)3)/-$1%/-%!!&1%-6%24)H4%/4'%3)*+)*I%5-+'%2"1%*-/%Q*-2*%
1-% 6"$C% S4'% 6-H#1% -6% /4)1% 2-$Q% 2"1% /-% N$'+)H/% /4'% +$#IMN$-/')*% )*/'$"H/)-*% -6% *-*M
Biomimetic Applications of Metal Systems Supported by Scorpionates

399
4J+$-O"5"/'%)*4)3)/-$1%2)/4-#/%/4'%*''+%6-$%'("3-$"/'%+$#I%1J*/4'1)1%-$%N$-/')*%1/$#H/#$'%
+'/'$5)*"/)-*C%S4'J%$'N-$/'+%/4'%3)*+)*I%-6%EM5'$H"N/-Q'/-*'%"*+%EM5'$H"N/-"5)+'%+$#I1%

)*%"%3)+'*/"/'%6"14)-*=%24)('%EM5'$H"N/-/4)-(1%3-#*+%'OH(#1):'(J%)*%"%5-*-+'*/"/'%5"**'$=%
H-*/$"$J%/-%N$)-$%'ON'H/"/)-*1%7&#'$/"%;%,-4'*=%>??>EC%F%24-('%1'$)'1%-6%N#3()H"/)-*1%3J%/4'%
1"5'% "#/4-$1% 'O/'*+'+% /4)1% H-*H'N/% /-% 6-#$% +)66'$'*/% I$-#N1% -6% H4'("/-$1b%
4J+$-OJNJ$)+)*-*'1=%NJ$-*'1=% 4J+$-OJNJ$)+)*'/4)-*'1%"*+%/4)-NJ$-*'1% 7&#'$/"%;%,-4'*=%
>??fA%&#'$/"%'/%"(C=%>??hA%&#'$/"%'/%"(C=%>??kA%&#'$/"%'/%"(C=%>??DA%u"H-31'*%'/%"(C=%>??eEC%g"H4%-6%
/4'% /'1/'+% 15"((% 5-('H#('1% 2"1% "3('% /-% +)1N("H'% /4'% 4J+$-O)+'% ()I"*+% )*% /4'%
XaB7NK
&4=!'
E
f
_\*Pa% 5-+'(% H-5N('O% -6% /4'% "H/):'% 1)/'%"*+% /-% H $+)*"/'% /4'% K)*H700E% )*% "%
3)+'*/"/'%6"14)-*%7&#'$/"%;%,-4'*=%>??fA%&#'$/"%'/%"(C=%>??hA%&#'$/"%'/%"(C=%>??DA%u"H-31'*%'/%
"(C=%>??eE%78)IC%@@3EC%S4'1'%H-5N-#*+1%$'N$'1'*/'+%/4'%K)*H%H4'("/)*I%N-$/)-*%-6%*'2%!!&%
)*4)3)/-$1% 7!&01E=% ("HQ)*I% /4'% H$)/)H"(%N'N/)+-5)5'/)H%3"HQ3-*'C% S4'% K)*H% 3)*+)*I% I$-#N1%
7\Bn1E%()1/'+%"3-:'%2'$'%6-#*+%/-%4":'%"%I$'"/'$%"66)*)/J%/4"*%"H'/-4J+$-O"5)H%"H)+%7FaFE%
6-$%/4'%K)*H700E%)-*%/4'%5-+'(%H-5N('OC%8#$/4'$5-$'=%/4'%)*4)3)/-$J%"H/):)/J%-6%/4'1'%\Bn1%
2"1%H-5N"$'+%2)/4%/4"/%-6%FaF%7&#'$/"%'/%"(C=%>??DEC%F((%/4'%*'2%H-5N-#*+1%2'$'%6-#*+%/-%
3'%5-$'%N-/'*/%)*4)3)/-$1%-6%!!&Mf%/4"*%FaF%7&#'$/"%'/%"(C=%>??hEC%S4)1%6)*"((J%$'1#(/'+%)*%
/4'%+':'(-N5'*/%-6%N-/'*/%"*+%1'('H/):'%NJ$-*'M3"1'+%)*4)3)/-$1%7&#'$/"%'/%"(C=%>??kEC%%
P/4'$%3)*+)*I%1/#+)'1%3J%/4'%,-4'*%I$-#N%$'N-$/'+%-*%N
@
MH $+)*"/)-*%6-$%K)*H%H-5N('O'1%
XaB7NK
&4=!'
E
f
_\*^%3'"$)*I%>M/4'*J(5'$H"N/"*=%1"()HJ("5)+'%"*+%/4)-1"()HJ()H%"H)+=%3#/%-*%N
>
M
H $+)*"/)-*% )*% H"1'% -6% 5'/4J(% 1"()HJ("/'=% 5'/4J(% /4)-1"()HJ("/'% -$% >M4J+$-J"H'/-N4'*-*'%

()I"*+1C% S4#1=%)/% 2"1% N-11)3('% /-% $':'"(% /4'%5-+'% -6% 3)*+)*I% -6% 5"*J%\Bn1% 7u"H-31'*% ;%
,-4'*=%>??hEC%0*/'$'1/)*I=%,-4'*%"*+%H-2-$Q'$1%"NN()'+%/4'%XaB7NK
&4=!'
E
f
_\*PaM6$"I5'*/%
/-% )+'*/)6J%\Bn1% 6-$%/4'% ('/4"(%6"H/-$% -6%"*/4$"O% 7u"H-31'*%'/% "(C=%>??DEC% l"4$'*Q"5N% "*+%
H-2-$Q'$% -31'$:'+% 3-/4=% "% 3)+'*/"/'% "*+% "% 5-*-+'*/"/'% H $+)*"/)-*% /-% "%
XaB7NK
&4=!'
E
f
_\*Pa%6$"I5'*/=%)*%H"1'%-6%>M5'$H"N/-N4'*-(%7S'Q'1/'%;%l"4$'*Q"5N=%>??DEC%
l"4$'*Q"5N%"(1-%$'N-$/'+%-*%6#$/4'$%1/#+)'1%$'I"$+)*I%/4'%H $+)*"/)-*%5"**'$%-6%DMQ'/-%
H"$3-OJ()H% "H)+1=% DM% "*+% EM+)Q'/-*'1=% EM5'$H"N/-% "5)*'1% "*+% "(H-4-(1% "1% 2'((% "1%
5'$H"N/-N$-N)-*)H%"H)+%7S'Q'1/'%;%l"4$'*Q"5N=%>??DEC%
j'H'*/%1/#+)'1%/$J%/-%"//"H4%6#*H/)-*"(%I$-#N1%/-%/4'%1H-$N)-*"/'%()I"*+1%-6%/4'%K)*H%5-+'(1=%
)*%-$+'$%/-%5)5)H%/4'%H"/"(J/)H"((J%)5N-$/"*/%I(#/"5)H%"H)+%-6%/4'%a
gOOa%K)*H)*%1'L#'*H'C%0*%
1-5'% 'O"5N('1=% /4'% H"$3-OJ("/'% H-5N('O% XaB7NK
,P>g/=!'
E
f
_\*7a
>
PE7PFHE% "*+% /4'%"5)+"/'%
H-5N('O% XaB7NK
8#=!'
E
f

_\*7a
>
PE7ca,P,8
f
E=% '1/'$% -$% 6#$J(% 6#*H/)-*"()/)'1% 6-$5% 4J+$-I'*%
3$)+I'1% /-%2"/'$% -$%"*% "5)+"/'=% $'1N'H/):'(J%78)IC%@@HE% 7a"55'1% '/%"(C=% >??>A%!"(+-*"+-%
,"(:-%;%l"4$'*Q"5N=%>??DEC
%
,4'("/)*I%()I"*+1%3'(-*I)*I%/-%/4'%N-(J7NJ$"K-(J(E3-$"/'1%H"*%3'%$'I"$+'+%"1%$'("/):'(J%hard
+-*-$% ()I"*+1% 4":)*I% /2-% -$% /4$''% "K-('% *)/$-I'*% "/-51% /4"/% H"*% 3'% )*:-(:'+% )*% 5'/"(%
H $+)*"/)-*C% S4'% "*"(-I-#1% N-(J75'/4)5"K-(J(E3-$"/'% "*)-*1% 75'/4)5"K-('% `% @M5'/4J(M
@HM)5)+"K-('M>7fHEM/4)-*'E%4":'%$'H'*/(J%3''*%$':)'2'+%3J%j'I()*1Q)%"*+%.N)H'$%7.N)H'$%;%
j'I()*1Q)=%>??dE%)*%-$+'$%/-%'ON(-$'%/4'%N$-N'$/)'1%-6%"%1-6/'$%H $+)*"/)-*%'*:)$-*5'*/%)*%"*%
"*)-*)H%()I"*+=%N$-:)+'+%)*%/4)1%H"1'%3J%/4)-*'%1#(6#$%"/-51%-6%/4'%5'/4)5"K-('%$)*I1C%S4'%
/2-% ()I"*+%1J1/'51% "(1-%+)66'$% 6#*+"5'*/"((J%)*%/4'%*#53'$%-6%"/-51%()*Q)*I%/4'%H'*/$"(%
3-$-*%"/-5%/-%/4'%+-*-$%"/-51C%S4'%1/$#H/#$"(%H-*1'L#'*H'1%-6%/4)1%+)66'$'*H'%"$'%+)1N("J'+%
)*% /4'% +)5'*1)-*1% -6% /4'% H4'("/'% $)*I1% 6-$5'+% #N-*% 5'/"(% H-5N('O% 6-$5"/)-*% "*+% /4'%
5-('H#("$% 1J55'/$J% I'*'$"/'+% "1% "% H-*1'L#'*H'% -6% /4'% H-*6-$5"/)-*1% "+-N/'+% 3J% /4'1'%
$)*I1C% S4#1=% H-5N('O'1% -6% /4'% /$)17NJ$"K-(J(E3-$"/'1% H-*/")*% /4$''% 1)OM5'53'$'+% H4'("/'%
$)*I1%"*+%/4'%$'1#(/)*I%H-5N('O'1%'O4)3)/%"%(-H"(%H $+)*"/)-*%'*:)$-*5'*/%-6%C
f:
%1J55'/$J=%
24)('% N-(J75'/4)5"K-(J(E3-$"/'1% H-5N('O'1% H-*/")*% /4$''% ')I4/M5'53'$'+% H4'("/'% $)*I1=%
Biomimetic Based Applications

400
/4#1%I'*'$"/)*I%"%5-$'%6('O)3('%/2)1/'+%-$%N$-N'(('$M()Q'%()I"*+%H-*6-$5"/)-*%"*+%(-H"(%C
f
%
1J55'/$JC%

S4'%XaB7/)5
j
E
f
_%()I"*+%1J1/'51%78)I%@>"E%N$-:)+'%"%#1'6#(%N("/6-$5%6-$%-3/")*)*I%1J*/4'/)H%
"*"(-I#'1% -6% K)*H% '*KJ5'1% "*+% N$-/')*1% /4"/%4":'%1#(6#$%$)H4%"H/):'%1)/'1%1#H4%kM
"5)*-(':#()*"/'%+'4J+$"/"1'%7F^FiE%"*+%/4'%F+"%icF%$'N")$%N$-/')*%7&'**'$Ma"4*=%>??eE%
78)I%R6EC%
%
B
N
N
N
N
N
N
H
S
S
S
R
R
R
B
N
N
N
N
N
N

H
S
S
S
Ph
Ph
Ph
Zn OH
(a)
(b)
%
8)IC%@>C%./$#H/#$'%-6b%"E%XaB7/)5
j
E
f
_%()I"*+1A%3E%XaB7/)5
&4
E
f
_\*Pa%H-5N('O=%1J*/4'/)H%
"*"(-I#'%-6%F^FiC%
S4'%/4$''%1#(6#$% +-*-$1%-6% /4'%XaB7/)5
j
E
f
_%()I"*+%1J1/'5% 5"J%3'% #1'+%/-% '5#("/'%/4'%/4$''%
HJ1/')*'% $'1)+#'1% )*% F^FiC% 0*% N"$/)H#("$=% /4'% K)*H% 4J+$-O)+'% H-5N('O% XaB7/)5
&4
E
f

_\*Pa%
H-5N('O%7B$)+I'2"/'$%;%&"$Q)*=%>??@E%78)I%@>3E%)1%/4'%6)$1/%/'/$"4'+$"(%K)*H%4J+$-O)+'%H-5N('O%
1#NN-$/'+%3J%"%X.f_%+-*-$%()I"*+%/-%3'%1/$#H/#$"((J%H4"$"H/'$)K'+%3J%ZM$"J%+)66$"H/)-*C%
S4'%5'H4"*)15%-6%"H/)-*%-6%F^Fi%)*:-(:'1%+)1N("H'5'*/%-6%/4'%"L#"%()I"*+%3J%/4'%1#31/$"/'%
kM"5)*-(':#()*)H%"H)+%7F^FEC%F%1)5N('%)*+)H"/)-*%/4"/%+)1N("H'5'*/%-6%/4'%"L#"%()I"*+%)*%1#H4%
"% H $+)*"/)-*% '*:)$-*5'*/% )1% 6"H)('%)1%N$-:)+'+%3J%N$-/-*"/)-*%-6%XaB7/)5
&4
E
f
_\*Pa% 2)/4%
a,(P
h%
)*% "H'/-*)/$)('=% )*% 24)H4% /4'% )*H)N)'*/% "L#"% ()I"*+% )1% +)1N("H'+% 3J% !',c% /-% I):'%
YXaB7/)5
&4
E
f
_\*7c,!'E]
q
%7B$)+I'2"/'$%;%&"$Q)*=%>???A%B$)+I'2"/'$%;%&"$Q)*=%>??@EC%%
.)5N('%1J*/4'/)H%"*"(-I#'1%6-$%/4'%X7,J1E
h
\*_%5-/)6%-6%/4'%F+"%N$-/')*%7&'**'$Ma"4*=%>??eE%
"$'% N$-:)+'+% 3J% /4'% /4)-("/'%H-5N('O'1% XaB7/)5
j
E
f
_\*.&4% 7j% `% &4% -$% /B#E=%)*% 24)H4% /4'%
XaB7/)5
j

E
f
_%()I"*+%1'$:'1%/4'%$-('%-6%/4'%/4$''%HJ1/')*'%$'1)+#'1%/4"/%$'5")*%3-#*+%/-%K)*H%
+#$)*I%/4'%H-#$1'%-6%/4'%"(QJ("/)-*%$'"H/)-*%7B$)+I'2"/'$%'/%"(C=%>???A%03$"4)5% '/%"(C=%>??kA%
!'(*)HQ%'/%"(C=%>??DEC%S4'%/4)-("/'%H-5N('O'1%XaB7/)5
j
E
f
_\*.,a
>
,7PEc7aE&4%7j%`%&4=%/B#E=%
24)H4% )*H-$N-$"/'% "*% cya% 4J+$-I'*% 3-*+)*I% 6#*H/)-*"()/J=% N$-:)+'% "% 5-$'% $'6)*'+%
1/$#H/#$"(%"*"(-I#'%6-$%/4'%F+"%N$-/')*%7!-$(-Q%'/%"(C=%>??kEC%%
F(QJ("/)-*%-6%"%K)*HyHJ1/')*'%/4)-("/'%$'1)+#'%)1%/4'%Q'J%1/'N%)*%/4'%5'H4"*)15%-6%"H/)-*%-6%
/4'% F+"% icF% $'N")$% N$-/')*% "*+% 5"J% 3'% 5-+'('+% 3J%/4'% $'"H/):)/J% -6% XaB7/)5
j
E
f
_\*.j%
/-2"$+1% "(QJ("/)*I%"I'*/1% 1#H4%"1%!'0C%0*+''+=%XaB7/)5
j
E
f
_\*.j% H-5N('O'1% $'"H/%$"N)+(J%
2)/4%!'0%/-%J)'(+%XaB7/)5
j
E
f
_\*0%"*+%j.!'%7B$)+I'2"/'$%'/%"(C=%>???A%03$"4)5%'/%"(C=%>??kA%
!'(*)HQ%'/%"(C=%>??DEC

%
F%H-5N$'4'*1):'%':"(#"/)-*%-6%/4'%$'"H/):)/J%-6%"%1'$)'1%-6%K)*H%/4)-("/'%
H-5N('O'1=% *"5'(J% XaB7NK
j=jU
E
f
_\*.j=% XaB7NKE
>
7/)5
j
E_\*.j=% XaB7NK
j
E7/)5
j
E
>
_\*.j=% "*+%
XaB7/)5
j
E
f
_\*.j=%)*%24)H4%/4'%1#NN-$/)*I%()I"*+%N$'1'*/1%Xc
f
_=%Xc
>
._=%Xc.
>
_%"*+%X.
f
_%+-*-$%

"$$"J1=%+'5-*1/$"/'1%/4"/%/4'%$'"H/):)/J%/-2"$+1%/4)-("/'%"(QJ("/)-*%)*H$'"1'1%3J%6-#$%-$+'$1%
-6%5"I*)/#+'%"H$-11%/4'%1'$)'1%7j-53"H4%'/%"(C=%>??DEC%
0*% "++)/)-*% /-% /4'% 2)+'1N$'"+% #1'% -6% /$)17NJ$"K-(J(E4J+$-3-$"/-% ()I"*+1=% /4')$%
3)17NJ$"K-(J(E4J+$-3-$"/-% H-#*/'$N"$/1=% Xa
>
B7NK
j=jU
E
>
_
M
=% 2'$'% '5N(-J'+% /-% N$'N"$'% /4$''M
Biomimetic Applications of Metal Systems Supported by Scorpionates

401
H $+)*"/'%+'$):"/):'1=%'CIC%Xa
>
B7NK
j=jU
E
>
_\*j=%7n-$$'((%'/%"(C=%@dd?A%^ *'J%'/%"(C=%@ddkE%/4"/%
5"J%3'%6#*H/)-*"()K'+%3J%)*1'$/)-*%-6%#*1"/#$"/'+%5-('H#('1%7'CIC%j
>
,P=%,P
>
%"*+%j
>
,.E%)*/-%
/4'%Bya%I$-#N%/-% -3/")*%H-5N-#*+1%/4"/%6'"/#$'% *'2%6"H)"((J%/$)+'*/"/'%Xc

>
P_%"*+% Xc
>
._%
+-*-$%()I"*+1%/4"/%4":'%N-/'*/)"(% 6-$%5-+'()*I%H'$/")*% K)*H%'*KJ5'1%7n-$$'((% '/%"(C=% @dd?A%
i-2()*I% ;% &"$Q)*=% @ddDA% n4-14% ;% &"$Q)*=% @ddREC% l"4$'*Q"5N% 1J*/4'1)K'+% /4'%
3)17NJ$"K-(J(E7/4)-)5)+"K-(J(E3-$"/'% ()I"*+1=% "1% Xc
>
._% +-*-$% ()I"*+1% *"5'(J%
XaB7NK
O
E
>
7/)5
O
E_
M
%78)IC%@f"E%7B'*Q5)(%'/%"(C=%>??hEC%
S4'% Xc.
>
_% +-*-$% 3)17/4)-)5)+"K-(J(E7NJ$"K-(J(E3-$"/'% ()I"*+1% 7."*/)*)% '/% "(C=% >?@?E=%
XaB7NK
O
E7/)5
O
E
>
_
M
=% H"*%3'% N$'N"$'+%'11'*/)"((J%3J% /4'%1"5'% N$-H'+#$'%#1'+% 6-$%/4'% 1N'H)'1%

XaB7NK
O
E
f
_
M
%"*+%XaB7/)5
O
E
f
_
M
=%24)H4%H-*1)1/1%-6%/4'%4)I4M/'5N'$"/#$'%$'"H/)-*%3'/2''*%pBa
h
%
"*+% "% 1/-)H4)-5'/$)H% "5-#*/% -6% /4'% NJ$"K-('% "*+r-$% /4)-)5)+"K-('C% S4'% ()I"*+%
^)XaB7NKE7/)5
!'
E
>
_% 78)IC% @f3E% 4"1% 3''*% N$'N"$'+% 3J% &"$Q)*% "*+% "NN()'+% 1#HH'116#((J% 6-$%
5-+'()*I%"1N'H/1%-6%/4'%3)-)*-$I"*)H%H4'5)1/$J%-6%K)*H%'*KJ5'1C%S4'%5-('H#("$%1/$#H/#$'%-6%
XaB7NKE7/)5
!'
E
>
_\*0% 2"1%+'/'$5)*'+% 3J%ZM$"J% +)66$"H/)-*=% /4'$'3J%+'5-*1/$"/)*I%/4"/%/4'%
H-5N('O% )1% )*+''+% 5-*-*#H('"$% 2)/4% "% +)1/-$/'+% /'/$"4'+$"(% H $+)*"/)-*% I'-5'/$J% /4"/%
$'1'53('1%/4'%"H/):'%1)/'%-6%^Fia%7p)53()*%'/%"(C=%@ddeA%p)53()*%'/%"(C=%@dddA%p)53()*%'/%"(C=%
>???EC%

%
B
N
N
H
N
N
N
S
R
N
R=
t
Bu or
i
Pr
B
N
N
H
N
N Me
S
N
S
Me
N
(a)
(b)
B

N
NN
N
N
N
H
Se
Se
Se
R
R
R
(c)
%
8)IC%@fC%./$#H/#$'%-6%"E%XaB7NKE
>
7/)5
j
E_
M
=%3E%XaB7NKE7/)5
!'
E
>
_
M
%"*+%HE%XaB7.')5
j
E
f

_
M
%()I"*+1C%
F*%)5N-$/"*/%+':'(-N5'*/% 2)/4%$'1N'H/% /-%/4'% #1'%-6%/4)1%H("11% -6%Xc.
>
_%+-*-$% ()I"*+1%2"1%
N$-:)+'+% 3J% )1-("/)-*% -6% /4'% '/4"*-(% H-5N('O=% YXaB7NK
&4=!'
E7/)5
-MF*
E
>
_\*7aPg/E],(P
h
C
g/Pa%
7.''3"H4'$% '/% "(C=% >??@A% .4#% '/% "(C=% >??fA% 03$"4)5% '/% "(C=% >??kE% 7/)5
-MF*
%`%@M7-M"*)1J(EM>M
/4)-)5)+"K-('E%24)H4%N$-:)+'1%/4'%3'1/%1/$#H/#$"(%5-+'(%/-%+"/'%6-$%^FiaC%0*/'$'1/)*I(J=%/4'%
1#(6#$%$)H4%H $+)*"/)-*%'*:)$-*5'*/%N$-:)+'+%3J%N-(J7/4)-)5)+"K-(J(E3-$"/'%()I"*+%1/"3)()K'1%
H $+)*"/)-*% -6% /4'%"(H-4-(% /-%K)*H=% /4'$'3J% 1#II'1/)*I%/4"/% -*'%-6% /4'% $'"1-*1%24J% ^Fia%
#/)()K'1% "% 1#(6#$% $)H4% H $+)*"/)-*% '*:)$-*5'*/% )1% /-% N$-5-/'% H $+)*"/)-*% -6% /4'% "(H-4-(%
$'("/):'% /-% /4"/% -6% 2"/'$C% F% $'H'*/% "*+% 1#31/"*/)"(% $':)'2% 3J% uC% j'I()*1Q)% "*+% !C% iC% .N)H'$%
7j'I()*1Q)%;%.N)H'$=%>??dE H-:'$1%"(5-1/%"((%"1N'H/1%-6% H4'5)1/$J%-6% 5'/4)5"K-('%3"1'+% 1-6/%
1H-$N)-*"/'% ()I"*+1% 2)/4% 1N'H)"(% $'6'$'$'*H'% /-% /4')$% #1'% )*% 3)-5)5'/)H% H4'5)1/$J% 7"(HC%
+'4J+$-I'*"1'=% F+"% $'N")$% N$-/')*1=% kM"5)*-(':#()*"/'% +'4J+$"/"1'=% 1#(6)/'% -O)+"1'=%
4J+$-I'*"1'=%!'$BE%"*+%/4')$%'5'$I)*I%#1'%"1%$"+)-N4"$5"H'#/)H"(1%7$4'*)#5=%/'H4*'/)#5EC%
.)*H'% /4'% N-(J7/4)-)5)+"K-(J(E3-$"/'% ()I"*+1% 7n"$*'$% '/% "(C=% @ddDE% 4":'% N$-:'*% /-% 3'%
:'$1"/)('=%2)/4%"%("$I'%:"$)'/J%-6%XaB7/)5

j
E
f
_
M
%+'$):"/):'1%4":)*I%3''*%N$'N"$'+=%&"$Q)*%'/%"(C%
'*:)1)-*'+% /4"/% "% 1)5)("$% 1'$)'1% -6% ()I"*+1% /4"/% 6'"/#$'1% "*% .'
f
M+-*-$% -$% .'
>
M+-*-$% "$$"J%
14-#(+% 3'% "HH'11)3('% "*+% /4'$'3J% N$-:)+'% "% 1'/% -6% ()I"*+1% 2)/4% 5-+)6)'+% '('H/$-*)H%
N$-N'$/)'1% 7!)*-#$"% '/% "(C=% >??DEC% 0*+''+=% /4'% /$)17>M1'('*-M@Mjy)5)+"K-(J(E3-$"/'% ()I"*+1=%
XaB7.')5
j
E
f
_%7n#K)'H%;%n#K)'H=%@ddhE%7j%`%!'=%!'1E=%4":'%3''*%-3/")*'+%78)IC%@fHE%"*+%#1'+%
/-% 1J*/4'1)K'% "% :"$)'/J% -6% 5'/"(% 7K)*H=% H"+5)#5% "*+% 5'$H#$JE% H-5N('O'1% 7^"*+$J% '/% "(C=%
Biomimetic Based Applications

402
>??eEC% S4'% $'("/'+% X.'
>
_M+-*-$% 3)17>M1'('*-M@M5'/4J()5)+"K-(J(E4J+$-3-$"/-% ()I"*+=%
Xa
>
B7.')5
!'
E

>
_
M
=%4"1%"(1-%3''*%1J*/4'1)K'+%"*+%)*:'1/)I"/'+%7^"*+$J%'/%"(C=%>??eA%^"*+$J%;%
&"$Q)*=% >??eEC% 0*/'$'1/)*I=% 24'$'"1% YXa
>
B7.')5
!'
E
>
_\*0]
>
%'O)1/1%"1%"%+)5'$=%/4'%1#(6#$%
H-#*/'$N"$/% Xa
>
B7/)5
!'
E
>
_\*0% )1% "% 5-*-5'$% 7p)53()*% '/% "(C=% @ddeA% p)53()*% '/% "(C=% >???EC%
F*-/4'$%)*/'$'1/)*I%"1N'H/%-6%YXa
>
B7.')5
!'
E
>
_\*0]
>
%)1%/4"/%/4'%3$)+I)*I%'*/)/J%)1%-*'%-6%/4'%>M
1'('*-M@M5'/4J()5)+"K-(J(%I$-#N1%$"/4'$%/4"*%/4'%4"()+'%()I"*+1C%

.':'$"(%"//'5N/1%/-%5-+'(%/4'%5-*-*#H('"$%"H/):'%1)/'%2)/4%15"((%3)-5)5'/)H%K)*H%H-5N('O'1%
'*+'+% ')/4'$% )*% 3)1()I"*+% H-5N('O'1% X\*^
>
_% -$% /4'% 6-$5"/)-*% -6% -()I-M% -$% N-(JM*#H('"$%
H-5N('O'1%7&"$Q)*=%>??hEC%,C%uC%,"$$"*-%"*+%BC%.C%a"55'1%"NN()'+%3#(QJ%tertM3#/J(%I$-#N1%)*%
ortho N-1)/)-*%/-%"%N4'*-("/'%+-*-$%/-%-:'$H-5'%/4'1'%N$-3('51C%<)/4%/4')$%"*)-*)H%/$)N-+"(%
N,N,O%()I"*+%7fMtertM3#/J(M>M4J+$-OJMkM5'/4J(N4'*J(E3)17f=kM+)5'/4J(NJ$"K-(M@MJ(E5'/4"*'=%
Xa,7NK
!'>
E
>
7,
D
a
>
Pa7/B#E!'E_=% /4'J% -3/")*'+% 1':'$"(% /'/$"4'+$"(% K)*H% H-5N('O'1% 2)/4%
4"(-I'*-=%"H'/"/-%-$%/4)-("/-%()I"*+1%78)IC%@h"E
%
7a"55'1%;%,"$$"*-=%@dddEC%<)/4%/2-%*)/$-I'*%
+-*-$1%"*+%"*%-OJI'*%+-*-$%/4)1%()I"*+%)1%2'((%1#)/'+%/-%5)5)H%/4'%"H/):'%1)/'1%-6%/4'$5-(J1)*%
-$%H"$3-OJN'N/)+"1'%F=%"(/4-#I4%/4'%K)*H700E%)*%/4'1'%5-+'(1%)1%3-#*+%3J%"%N4'*-("/-%+-*-$%
)*1/'"+%-6%"%H"$3-OJ("/-%+-*-$%7.5)/4%'/%"(C=%>??fA%.5)/4%'/%"(C=%>??kEC%
%
%
8)IC%@hC%"E%./$#H/#$'%-6%Xa,7NK
!'>
E
>
7,
D

a
>
P7/B#E!'E_\*Z%H-5N('O'1A%3E%N
@
rN
>
%'L#)()3$)#5%)*%
4J+$-O"5"/-%H-5N('O'1C%
F(QJ(% K)*H% H-5N('O'1%3'"$)*I% :"$)-#1% 3)17NJ$"K-(M@MJ(E"H'/"/-% ()I"*+1%7a,7NK
j=jU
E
>
7,PPE
M
E%
-66'$%"*%'"1J%"HH'11%/-%3'//'$%1/$#H/#$"(%5-+'(%H-5N('O'1%6-$%K)*H%N'N/)+"1'1%2)/4%"%>Ma)1M@M
H"$3-OJ("/'%5-/)6C%./"$/)*I%6$-5%5'/4J(%H-5N('O'1%X7a,7NK
j=jU
E
>
7,PPE\*,a
f
_%1-%6"$%1':'$"(%
H-5N('O'1%2)/4%H"$3-OJ("/-M=%/4)-("/-M%"*+%"(1-%4J+$-O"5"/-M()I"*+1%4":'%3''*%-3/")*'+%3J%
5'/4"*'%$'('"1)*I%$'"H/)-*1%2)/4%H"$3-OJ()H%"H)+1=%/4)-(1%"*+%4J+$-O"5)H%"H)+1%7B'HQ%'/%"(C=%
>??@A%a'I'(5"**%'/%"(C=%>??fA%.5)/4%'/%"(C=%>??fA%.5)/4%'/%"(C=%>??kEC%FHH-$+)*I%/-%/4'%c!j%
1N'H/$"%/4'1'%H-5N('O'1%-6/'*%'O4)3)/%"%N
@
rN
>

%'L#)()3$)#5%78)IC%@h3EC%%
S4)-("/'1=%H"$3-OJ("/'1%"*+%4J+$-O"5"/'1%"$'%/4'%5-1/%H-55-*%K)*H%3)*+)*I%I$-#N1%#1'+%
)*% K)*H% N'N/)+"1'% )*4)3)/-$1%1#H4%"1%F,g%)*4)3)/-$1C%!-1/%-6%/4'1'%5-+'(1%6-$%
H"$3-OJN'N/)+"1'1%4":'%3''*%H4"$"H/'$)1'+%3J%ZM$"J%1/$#H/#$'%+'/'$5)*"/)-*1%7B'HQ%'/%"(C=%
>??@A% a'I'(5"**%'/% "(C=%>??fA% .5)/4%'/% "(C=%>??fA% .5)/4%'/% "(C=%>??kE=% /4'%5-+'(% H-5N('O'1%
4'(N)*I%/-%+':'(-N%*'2%K)*H%3)*+)*I%I$-#N1%6-$%N-/'*/)"(%N'N/)+"1'%)*4)3)/-$1C%
3.3 Other relevant biomimetic metal systems
0*% $'H'*/% J'"$1% H-5N('O'1% -6% 1H-$N)-*"/'% ()I"*+1% 2'$'% 1#HH'116#((J% #1'+% /-% 5)5)H% /4'%
"H/):)/J%-6%'*KJ5'1%H-*/")*)*I%:"$)-#1%5'/"(1%1#H4%"1%:"*"+)#5=%5"*I"*'1'=%)$-*=%H-3"(/=%
*)HQ'(=%5-(J3+'*#5%"*+%/#*I1/'*C%
VanadiumC%F*%)5N-$/"*/%")5%-6%/4'%:"*"+)#5%H4'5)1/$J%)1%/-%5-+'(%:"*"+)#5%4)1/)+)*'%
)*/'$"H/)-*1% /4-#I4/% /-% 3'% N$'1'*/% )*% /4'% '*KJ5'% 4"(-N'$-O)+"1'% 7B#/('$=% @dddEC% S4'%
Biomimetic Applications of Metal Systems Supported by Scorpionates

403
-HH#$$'*H'%-6%:"*"+)#5%)*%():)*I%1J1/'51%"*+%/4'%$'(':"*/%H4'5)1/$J%4":'%3''*%$':)'2'+%
7g/)'**'=%@ddDEC%j'H'*/(J=%/4'%:"*"+)#5%H-5N('O'1%-6%I'*'$"(%/JN'%^lP7P
>
EXaB7NKE
f
_7aNKE`%
"*+%^lP7P
>
EXNKB7NKE
f
_7aNKE`%2'$'%1J*/4'1)K'+=%H4"$"H/'$)K'+%"*+%)*+)H"/'+%"1%5-+'(%6-$%
4"(-N'$-O)+"1'%7la&PE%'*KJ5'1%7a-(5'1%;%,"$$"*-=%@dd@A%Z)*I%'/%"(C=%>??eE=%/4"/%"$'%"3('%
/-% H"/"(JK'% /4'% -O)+"/)-*% -6% 4"()+'1% /-% H-$$'1N-*+)*I% 4JN-4"(-#1% "H)+1=% 24)H4% $'"+)(J%
#*+'$I-%4"(-I'*"/)-*%-6%-$I"*)H%1#31/$"/'1%-$%H-*:'$1)-*%-6%4J+$-I'*%N'$-O)+'%/-%1)*I('/%
-OJI'*% "*+% I'*'$"/)-*% -6% 4"()+'1C% S4'% N1'#+ H/"4'+$"(% l70lE% H-5N('O'1% 2)/4%

/$)17NJ$"K-(J(E3-$"/'% ()I"*+1=% ^XaB7NKE
f
_l7PE,(`
C
i!8% "*+% ^XaB7NK
!'=!'
E
f
_l7PE,(`
C
i!8%
2'$'%6-#*+%/-%'O4)3)/%N-/'*/%3)-(-I)H"(%"H/):)/J%7n4-14%'/%"(C=%@dddEC%
ManganeseC% !)5)HQ)*I% /4'% "H/):)/J% -6% 5"*I"*'1'% 1#N'$-O)+'% +)15#/"1'% "*+% -6% :"$)-#1%
3)*#H('"$% 5"*I"*'1'% '*KJ5'1% "H/):'% )*% $'+-O% 6#*H/)-*1M% 2"1% "NN$-"H4'+% 2)/4%
XaB7NK
)&$=)&$
E
f
_!*7PBKE%"*+%$'("/'+%3)*#H('"$%H-5N('O'1%7.4'"/1%'/%"(C=%@dReA%p)/"G)5"%'/%"(C=%
@dd@A%p)/"G)5"%'/%"(C=%@ddfE%1#H4%"1%XaB7NK
)&$=)&$
E
f
_!*
>
7ǍM8PBKE
f
7aNK
)&$=)&$
E

>
%7.)*I4%'/%"(C=%>??DE.
i'4J+$"/):'%H-*+'*1"/)-*%-6%/4'%+)*#H('"$%!*7000EM3)17ǍM-O-E%H-5N('O%^XaB7NK
)&$=)&$
E
f
_!*7ǍM
PE`
>
% 2)/4% a
>
P
>
%)*%/4'%N$'1'*H'%-6%>M5'/4J()5)+"K-('% J)'(+'+% /4'% )5)+"K-('MH-*/")*)*I%
N'$-O-5"*I"*'1'7000E% H-5N('O%XaB7NK
)&$=)&$
E
f
_!*7Ǎ
>
MP
>
E7a)5
!'
EC% S4)1%H-5N('O% 5"J% 5)5)H%
/4'%'11'*/)"(%$-('%-6%/4'%TT+)1/"(UU%4)1/)+)*'%$'1)+#'%)*%/4'%4'5-I(-3)*r5J-I(-3)*%7.)*I4%'/%
"(C=%>??DEC%
IronC% 0*% /4'% "$'"% -6% )$-*MH-*/")*)*I% '*KJ5'1=% /4'% 3'4":)-$% -6% /4'% -O-M3$)+I'+% +)M)$-*%
'*KJ5'% 4'5'$J/4$)*% 2"1% "NN$-O)5"/'+% 2)/4% H-5N('O'1% 1#H4% "1% YXaB7NKE
f

_8']
>
7zMPE7zM
PP,jE%"*+%YXaB7NKE
f
_8']
>
7zMPaE7zMPP,jE%7F$51/$-*I%;%^)NN"$+=%@dRhA%F$51/$-*I%'/%"(C=%
@dRhA% ,K'$*#1K'2)HK% '/% "(C=% @dReE, 24)('% /4'% H-5N('O% XaB7NK
)&$=)&$
E
f
_8'7PBKE7,a
f
,cE% 2"1%
$'I"$+'+% "1% "% 1J*/4'/)H% 5-+'(% 6-$% /4'% +)-OJI'*% 3)*+)*I% 1)/'% -6% *-*4'5'% )$-*% N$-/')*1%
7p)/"G)5"%'/%"(C=%@dd?E. S4'%"()N4"/)H%ǂMQ'/-%H"$3-OJ("/'%XaB7NK
&4=&4
E
f
_8'
00
7P
>
,,7PE,a
f
E%"*+%
/4'%H"$3-OJ("/'%H-5N('O'1%XaB7NK
&4=&4
E

f
_8'
00
7PBKE%"*+%aB7NK
&4=&4
E
f
_8'
00
7PFHE7aNK
&4>
E_%2'$'%
1J*/4'1)K'+% "*+% 1/#+)'+% /-% H("$)6)'+% /4'% Q'J% $-('% /4"/% /4'% ǂMQ'/-% 6#*H/)-*"()/J% N("J1% )*%
-OJI'*%"H/):"/)-*%3J%ǂMQ'/-%"H)+M+'N'*+'*/%)$-*%'*KJ5'1%7!'4*%'/%"(C=%>??fEC%S4'%H-5N('O%
XaB7NK
)&$=)&$
E
f
_8'7PP&/*E_%7&/*%`%&/'$)*N'$-O-E%4"1%3''*%+'1H$)3'+%"1%"%$'(':"*/%5-+'(%6-$%
N-/'*/)"(% )*/'$5'+)"/'1% )*% N/'$)*M+'N'*+'*/% 4J+$-OJ("1'1% 7^'4*'$/% '/% "(C=% >??fEC% P/4'$%
$'("/'+% H-5N('O'1% 2'$'% $'I"$+'+% "1% 1/$#H/#$"(% "*+% 6#*H/)-*"(% 5-+'(1% -6% H"/'H4-(%
+'4J+$-I'*"1'1% 7PI)4"$"% '/% "(C=% @ddRE "*+% "1% N'$-O-% )*/'$5'+)"/'% )*% /4'% 5'/4"*'%
5-* OJI'*"1'% 4J+$-OJ("1' $'"H/)-*% HJH('% 7p)5% ;% ^)NN"$+=% @ddDEC% S4'% H-5N('O
XaB7NK
!'=!'
E
f
_8'7H"/'H4-("/'E7aNK
!'=!'
E%4"1%3''*%N$'N"$'+%"*+%)/1%$'"H/):)/J%/-2"$+%-OJI'*%

)*:'1/)I"/'+%"1%5-+'(%6-$%/4'%H"/'H4-(%+)-OJI'*"1'1%7["/%'/%"(C=%>??fEC%
CobaltC%S4'%H-3"(/%H-5N('O'1%XaB7NK
j
E
f
_,-7ZE%7Z%`%c
f
=%c,.A%XaB7NK
j
E
f
_%`%XaB7NK
!'=!'
E
f
_%-$%
XaB7NK
&4
E
f
_E% 4":'% 3''*% #1'+% "1% H"/"(J1/1% )*% /4'% 3)H"$3-*"/'% +'4J+$"/)-*% $'"H/)-*% )*% /4'%
N$'1'*H'%-6%)*4)3)/-$1%7.#*%'/%"(C=%>??hA%.#*%'/%"(C=%>??hEC%
NikelC% !-*-5'$)H% 6):'MH $+)*"/'% c)MHJ1/')*'% H-5N('O'1% -6% /$)17f=kM+)1#31/)/#/'+%
NJ$"K-(J(E3-$"/'1% 7XaB7NK
!'=!'
E
f
_
M
%"*+%XaB7NK

&4=!'
E
f
_
M
E% "*+% ^MHJ1/')*'% 7+)'/4J(% '1/'$% "*+%
"5)*-%"H)+%6-$51E%2'$'%1/#+)'+%"1%3')*I%-6%$'(':"*H'%/-%/4'%*)HQ'(%H-5N-*'*/%-6%/4'%"H/):'%
1)/'%)*% 1':'$"(%4J+$-I'*"1'%'*KJ5'1=%24)H4% N"$/)H)N"/'%)*%/4'%3)-MI'*'$"/)-*%-6%4J+$-I'*%
"*+%5'/4"*'=%"1%2'((%"1%)*%*)/$-I'*%6)O"/)-*%7i'1$-H4'$1%'/%"(C=%@dddEC%aJ+$-/$)17fMN4'*J(MkM
5'/4J(NJ$"K-J(E3-$"/-*)HQ'(700E% H-5N('O'1% 2)/4% -$I"*-O"*/4"/'% -$% +)/4)-H"$3"5"/'%
H-()I"*+1% 'L#)()3$"/'% 3'/2''*% Nj
>
M% "*+% Nj
f
MH4'("/)-*% 5-+'1% -6% /4'% 1H-$N)-*"/'% ()I"*+% )*%
1-(#/)-*=% H-**'H/)*I% c
>
.
>
%1L#"$'MN("*"$%"*+%c
f
.
>
%NJ$"5)+"(%()I"*+%6)'(+1%"*+%"%1N)*%
H$-11-:'$C%S4'%H-5N('O'1%"(1-%'O4)3)/%L#"1)M$':'$1)3('%-O)+"/)-*1%"/%(-2%"*-+)H%N-/'*/)"(1=%
/4#1% 5-+'()*I% /4'% 1/$#H/#$'=% +J*"5)H1=% "*+% $'+-O% $'"H/):)/J% -6% /4'% $'+#H'+% *)HQ'(%
Biomimetic Based Applications

404
1#N'$-O)+'%+)15#/"1'%7c).PiE%"H/):'%1)/'%7!"%'/%"(C=%>??REC%S4'%#1'%-6%"*"(-I-#1%1/'$)H"((J%

('11% +'5"*+)*I% 4J+$-/$)17f=kM+)5'/4J(NJ$"K-(J(E3-$"/'% ()I"*+1% "((-2% /-% -3/")*%
N"$"5"I*'/)H% N'*/"H $+)*"/'% c
f
.
>
%1/$#H/#$'1%6-$%3-/4%O"*/4"/'%"*+%+)/4)-H"$3"5"/'%H-M
()I"*+1% )*% /4'% 1-()+% 1/"/'% 7!"% '/% "(C=% >??dEC% a-2':'$=% /4'1'% 1/$#H/#$'1% 'O4)3)/% :"$)"3('%
+)1/-$/)-*% /-2"$+1% "% /$)I-*"(% 3)NJ$"5)+"(% I'-5'/$J% +#'% /-% '*4"*H'+% $-/"/)-*% -6% /4'%
+)/4)-"H)+% H4'("/'1% $'("/):'% /-% /4'% 1H-$N)-*"/'% 6"H'C% g:)+'*H'% 2"1% 6-#*+% *-*'/4'('11% 6-$%
$'/'*/)-*% -6% /4'% 1N)*% 'L#)()3$)#5% "*+% -*'M'('H/$-*% $'+-O% H-#N('1% )*% 1-(#/)-*C% S4'1'%
-31'$:"/)-*1% "((-2% /-% H-*1)+'$% 1/'$)H% '66'H/1% "$)1)*I% 6$-5% "% N"//'$*% -6% fMNJ$"K-('% $)*I%
1#31/)/#/)-*%-*%/4'%1/$#H/#$'%"*+%+J*"5)H1%-6%/4'%3)-5)5'/)H%H-5N('O'1C%
Molybdenum and tungstenC%S4'%I$-#N%D%'('5'*/1%5-(J3+'*#5%"*+%/#*I1/'*%"$'%/4'%-*(J%
1'H-*+%"*+%/4)$+%$-2%/$"*1)/)-*%5'/"(1%'11'*/)"(%/-%"((%6-$51%-6%()6'%-*%g"$/4C%!-(J3+'*#5%)1%
6-#*+%"/%/4'%"H/):'%1)/'1%-6%*)/$-I'*"1'%"*+%"((%-6%/4'%5-$'%/4"*%k?%Q*-2*%!-M!&S%'*KJ5'1%
7!&S%`%T5-(J3+-N/'$)*U%-$%!'/"(M3)*+)*I%&/'$)*%'*'M@=>M+)S4)-("/'E%/4"/%N("J%:)/"(%$-('1%)*%
N("*/=% "*)5"(=% "*+% 4#5"*% 4'"(/4=% /4'% H"$3-*=% 1#(6#$=% "*+% *)/$-I'*% HJH('1=% 3)-6''+3"HQ%
1J1/'51=%"*+%/4'%H-*/$-(% -6%I(-3"(%H()5"/'%7a)(('=% @ddDA% S#**'J%'/%"(C=%>??hEC%S4'%!-M!&S%
'*KJ5'1%6'"/#$'%"H/):'%1)/'1%H-5N-1'+%-6%"%1)*I('%75-*-*#H('"$E%!-%"/-5%H $+)*"/'+%3J%
-*'%-$%/2-%!&SM3"1'+%()I"*+1A%/#*I1/'*%)1%"(1-%"11-H)"/'+%2)/4%!&SM3"1'+%()I"*+1%)*%"((%)/1%
Q*-2*%3)-(-I)H"(%5"*)6'1/"/)-*1C%,4'5)H"(%"NN$-"H4'1%/-%5-(J3+'*#5%'*KJ5'%1)/'1%4":'%
3''*%+)$'H/'+%/-2"$+%5)5)HQ)*I%"%N-$/)-*%-6%/4'%1/$#H/#$"(%H'*/'$%)*%-$+'$%/-%"1H'$/")*%/4'%
$-('%-6%/4"/%N"$/)H#("$%6'"/#$'%-6%/4'%H'*/'$%-*%/4'%H4'5)H"(%$'"H/):)/J%"*+%/4'%1N'H/$-1H-N)H%
N$-N'$/)'1%-6%/4'%H'*/'$C%gO)1/)*I%1-#$H'1%7a-(5=%@dReA%a-(5=%@dd?A%g*'5"$Q%;%[-#*I=%@ddhA%
./)'6'(=% @ddeA% [-#*I% ;% <'++=% @ddeA% [-#*I% ;% [-#*I=% @ddeA% a)(('% '/% "(C=% @ddRA% 8)1H4'$% ;%
B#$I5"J'$=%>??>A%g*'5"$Q%'/%"(C=%>??hE%N$-:)+'%3"HQI$-#*+%/-%'"$()'$%2-$Q%)*%/4)1%"$'"C%S4'%
'*KJ5-(-IJ% "*+% -/4'$% "1N'H/1% -6% 5-(J3+'*#5%3)-H4'5)1/$J%4":'%3''*%'O/'*1):'(J%
H-*1)+'$'+% '(1'24'$'% 7a)(('=% @ddDA% a)(('=% >??>A% !-#$"% '/% "(C=% >??hA% B$-*+)*-% '/% "(C=% >??DA%
.H42"$K% ;% !'*+'(=% >??DEC% S4'% "H/)-*% -6% -OJI'*M"/-5% /$"*16'$% '*KJ5'1% 24)H4% H-*/")*%
/$)17NJ$"K-(J(E3-$"/'M3"1'+%5-(J3+'*#5%"*+% /#*I1/'*%N/'$)*%'*KJ5'% 5-+'(1%H'*/$'1% 2"1%

+)1H#11'+%)*%"%$':)'2%-6%[-#*I%"*+%<'++%7[-#*I%;%<'++=%@ddeEC%0*%"%$'H'*/%$':)'2%2'%
"*"(JK'+%/4'%-:'$"((%N$-I$'11%-*%1J*/4'/)H%"*"(-I#'1%-6%/4'1'%'*KJ5'%H'*/'$1%"*+%+)11'H/'+%
/4'% H-*/$)3#/)-*1%-6% 1J1/'51%)*% 24)H4%H $+)*"/)-*% 1N4'$'1%H-*/")*%N-(J7NJ$"K-(J(E3-$"/'%
()I"*+1%7&'((')%'/%"(C=%>??dEC%%
3.3.1 Nitrogenase and related synthetic models having pyrazolylborate anions
S4'%5-1/%'O/'*1):'(J%1/#+)'+%*)/$-I'*"1'%'*KJ5'%H-*/")*1%)$-*%"*+%5-(J3+'*#5%5'/"(1=%
"*+%)1%H"(('+%5-(J3+'*#5%*)/$-I'*"1'%7B#$I'11%;%^-2'=%@ddDA%.5)/4=%@dddA%,4$)1/)"*1'*%'/%
"(C=%>??@A%0I"$"14)%;%.''6'(+/=%>??fEC 0*%I$-2/4%H-*+)/)-*1%24'$'%5-(J3+'*#5%H-*H'*/$"/)-*%
)1%(-2=%"%*)/$-I'*"1'%+'N'*+)*I%-*%)$-*%"*+%:"*"+)#5%)1%'ON$'11'+%7g"+J=%@ddDA%g"+J=%>??fA%
j'4+'$=%>??fA%,$"*1%'/%"(C=%>??hEC%<4'*%3-/4%5-(J3+'*#5%"*+%:"*"+)#5%"$'%#*":")("3('=%"%
/4)$+%/JN'%-6%*)/$-I'*"1'%)1%'ON$'11'+%/4"/%H-*/")*1%)$-*%"1%/4'%-*(J%/$"*1)/)-*%5'/"(%7g"+J=%
@ddDA%p$"4*%'/%"(C=%>??>A%.)'5"**%'/%"(C=%>??>EC%!-M*)/$-I'*"1'%)1%/4'%-*(J%-*'%6-$%24)H4%3-/4%
+'/")('+%1/$#H/#$"(%"*+%5'H4"*)1/)H%+"/"%"$'%":")("3('%7a-2"$+%;%j''1=%@ddDA%!"J'$%'/%"(C=%
@dddA%g)*1('%'/%"(C=%>??>EC%S4'%'*KJ5"/)H%H-5N('O%H-5N$)1'1%/2-%N$-/')*1b%/4'%)$-*MN$-/')*%
78'MN$-/')*E%"*+%/4'%5-(J3+'*#5%)$-*MN$-/')*%7!-8'MN$-/')*EC%S4'$'%"$'%/4$''%H"/"(J/)H"((J%
*'H'11"$J%5'/"(y1#(6#$%H(#1/'$1%)*%)$-*y5-(J3+'*#5%*)/$-I'*"1'b%/4'%8'
h
.
h
%H(#1/'$%)*%/4'%8'M
N$-/')*=%/4'%8'!-MH-6"H/-$%"*+%/4'%&MH(#1/'$C%S4'%)$-*y5-(J3+'*#5%H-6"H/-$%78'!-MH-E%-6%
*)/$-I'*"1'%7p)5%;%j''1=%@dd>A%,4"*%'/%"(C=%@ddfA%&'/'$1%'/%"(C=%@ddeA%!"J'$%'/%"(C=%@dddA%g)*1('%
'/%"(C=%>??>E%)1%-*'%-6%/4'%5-1/%6"1H)*"/)*I%'O4)3)/1%)*%3)-)*-$I"*)H%H4'5)1/$J=%3'H"#1'%)/%)1%
Biomimetic Applications of Metal Systems Supported by Scorpionates

405
4'$'% /4"/%/4'% '*KJ5'% 1-5'4-2%H"/"(J/)H"((J% H('":'1% /4'% 1/$-*I% /$)N('% 3-*+% -6% c
>
%/-%I):'%
"55-*)"%7^-2'%'/%"(C=%@ddfEC%S4'%8'!-MH-%4"1%3''*%-31'$:'+%)*%/4$''%$'+-O%1/"/'1%7&'/'$1%'/%

"(C=%@ddeA%!"J'$%'/%"(C=%@dddA%.H45)+%'/%"(C=%>??>EC%S2-%+)66'$'*/%1/$#H/#$'1%"$'%Q*-2*%6-$%/4'%
&MH(#1/'$%"*+% "$'%"11)I*'+% /-%+)66'$'*/% H(#1/'$%H-$'% -O)+"/)-*%1/"/'1C%0*%/4'%$'+#H'+%-$% &
c
%
76#((J% $'+#H'+E% 1/"/'=% /4'% 8'
R
.
e
%H(#1/'$%H"*%3'%+'1H$)3'+%"1%/2-%8'
h
.
h
%H#3'1%14"$)*I%-*'%
H-55-*% 4'O"H $+)*"/'% 1#(6#$% "/-5=% /4'% )$-*% "/-51% 3')*I% ()*Q'+% /-% /4'% N$-/')*% 3J%
HJ1/')*"/'%()I"*+1=%/2-%-6%/4'5%3$)+I)*I%/4'%1#3H#3'1%78)IC%@k"EC%0*%/4'%-O)+)K'+%1/"/'%&
PZ
%
1/"/'%7&
>q
E=%-O)+)K'+%3J%/2-%'('H/$-*1%$'("/):'%/-%&
c
=%/4'%H'*/$"(%1#(6#$%"/-5%(-1'1%/2-%3-*+1%
2)/4% /2-% )$-*%"/-51% )*% -*'% -6%/4'% 1#3H#3'1=% /4#1% 3'H-5)*I% 5-$'%-N'*C% S4'% /'/$"4'+$"(%
H $+)*"/)-*%-6%/4'1'%/2-%)$-*%"/-51%)1%/4'*%H-5N('/'+%3J%'O/$"%()I"/)-*1%6$-5%*')I43-$)*I%
HJ1/')*'%-$%1'$)*'%$'1)+#'1%7&'/'$1%'/%"(C=%@ddeA%!"J'$%'/%"(C=%@dddA%g)*1('%'/%"(C=%>??>EC%
%
Fe
S
S
S

Fe
Fe
Fe
S
Fe
S
S
Fe
Fe
Fe
S
S
Cys
S
Cys
S
Cys
S
Cys
S
Cys
Fe
S
BH
N
N
NN
NN
S
M

Fe
Fe
S
S
S
Fe
M
S
Fe
S
Fe
S
S
SH
HS
B
H
NN
NN
NN
n-
M =MoorV
(a)
(b)

8)IC%@kC%"E%./$#H/#$'%-6%/4'%&MH(#1/'$1%-6%*)/$-I'*"1'%)*%/4'%$'+#H'+%1/"/'%X8'
R
7z
>
M.

,J1
E
>
7z
f
M
.E
D
7z
D
M.E_%H-$'=%7&M,(#1/'$=%&
c
%1/"/'EA%3E%5-(J3+'*#5M%-$%:"*"+)#5MH-*/")*)*I%&
c
MH(#1/'$%
/-N-(-I)H"(%"*"(-I#'%-6%/4'%&
c
%H(#1/'$%-6%*)/$-I'*"1'C%
.J*/4'/)H%H4'5)1/1%4":'%H$'"/'+%)$-*y1#(6#$%H(#1/'$1%/4"/%5)5)H%/4'%#*#1#"(%+)1/$)3#/)-*%-6%
)$-*%"/-51%)*%&
c
%7a#"*I%'/%"(C=%@ddeA%P1/'$(-4%'/%"(C=%@dddA%P1/'$(-4%'/%"(C=%>??@A%\4"*I%'/%"(C=%
>??>A%\4"*I%;%a-(5=%>??fA%\#-%'/%"(C=%>??fA%^''%;%a-(5=%>??hA%\4"*I%;%a-(5=%>??hEC%0*%
N"$/)H#("$% 5-*-5'$)H% H(#1/'$1%^XaB7NKE
f
_
>
!
>
8'

D
.
d
`
*M
A% 7!%`% !-=% *%`% fA% !% `%l=%*% `% hE%"$'%
1/"3)()K'+%3J%/4'%/$)17NJ$"K-(J(E3-$"/'%()I"*+=%14-2)*I%/4"/%/4'%H(#1/'$%/-N-(-IJ%6-#*+%)*%&
c
%
H"*%'O)1/%"1%"%6$''%'*/)/J%)*%1-(#/)-*%7\4"*I%'/%"(C=%>??>EC%%
S4'%1N'H)'1%)*%8)IC%@k3=%)1%"*%'O"5N('%-6%"%/-N-(-I)H"(%"*"(-I%-6%/4'%8'
R
.
e
%&MH(#1/'$%2)/4%/4'%
X!-
>
8'
D
.
e
_
kM
%H-$'=%)1-("/'+%"1%/4'%H$J1/"(()*'%g/
h
c
q
%1"(/%7\4"*I%'/%"(C=%>??>A%\4"*I%;%a-(5=%
>??fEC%
S4'% &MH(#1/'$% 1/$#H/#$'% H-#(+% 3'% 1/"3)()K'+% )*%-/4'$%5-('H#('1=%"*+%)*%N"$/)H#("$%/4'%

:"*"+)#5MH-*/")*)*I%&
c
MH(#1/'$%/-N-(-I)H"(%"*"(-I#'%)1%$'N-$/'+%7a"#1'$%'/%"(C=%>??>A%\4"*I%
'/%"(C=%>??>A%\#-%'/%"(C=%>??fE%78)IC%@k3EC%S4'%H(#1/'$1%4":'%"%H$J1/"((-I$"N4)H"((J%)5N-1'+%/2-M
6-(+%"O)1%24)H4%H-*/")*1%"/-5%Ǎ
D
M.%"*+%)1%N'$N'*+)H#("$%/-%/4'%8'
h
%N("*'%)*%/4'%H'*/'$%-6%/4'%
5-('H#('C%S4'%Ǎ
D
M.%"/-5%"*+% )/1%"11-H)"/'+%)*/'$"H/)-*1% H-*1/)/#/'% /4'%5-1/% 'O/$"-$+)*"$J%
N"$/%-6%/4'%1/$#H/#$'1%-6%/4'%H(#1/'$1%$'N-$/'+%)*%8)IC%@k3C%.'O/#N(JM3$)+I)*I%1#(6#$%"/-51%"$'%
*-/% #*N$'H'+'*/'+% )*% 1J*/4'/)H% H(#1/'$1=% 3#/% /4'J% "$'% $"$'(J% '*H-#*/'$'+C% F% 3'1/M6)/%
1#N'$N-1)/)-*% -6%/4'%l
>
8'
D
.
d
%H-$'%-6%lM1N'H)'1%)*%8)IC%@k3%2)/4%/4'%H-$'%"/-51%-6%/4'%&
c
%
H(#1/'$% -6% *)/$-I'*"1'% 7K. pneumoniae !-8'%N$-/')*E%7!"J'$% '/% "(C=% @dddE% ('"+1% /-% "*% $51%
+':)"/)-*%-6%?Cff%t%)*%"/-5%N-1)/)-*1%7^''%;%a-(5=%>??hEC%S4'%H-$$'1N-*+)*I%+':)"/)-*%6-$%
!-M1N'H)'1% )1%?CfR% tC% P*'% 1-#$H'% -6%/4'% +':)"/)-*% 3'/2''*%1J*/4'/)H% H(#1/'$1% "*+%/4'% &
c
%
H(#1/'$%)1%/4'%1)I*)6)H"*/(J%("$I'$%8'ï7Ǎ
D

M.Eï8'%"*I('%-6%@kRo%"*+%)/1%"//'*+"*/%'66'H/%-*%"/-5%
N-1)/)-*1%)*%/4'%*"/):'%H(#1/'$C%S4'%+)66'$'*H'1%-6%"%!-
>
8'
D
%-$%"%l
>
8'
D
%)*1/'"+%-6%"*%8'
R
%5'/"(%
H-*/'*/% "*+% /2-% Ǎ
>
M.% "/-51% )*1/'"+% -6% /2-% Ǎ
>
M.
,J1
%3$)+I'1%*-/2)/41/"*+)*IC%S4'$'6-$'=%
H(#1/'$1%$'N-$/'+%)*%8)IC%@k3%"$'%/4'%'OH'(('*/%'O"5N('1%-6%5-('H#("$%/-N-(-I)H"(%"*"(-I#'1%
-6%/4'%&
c
%H(#1/'$%-6%*)/$-I'*"1'C%
Biomimetic Based Applications

406
a)I4M*#H('"$)/J%5'/"(M1#(6#$%H(#1/'$1%5"J%6#*H/)-*%"1%N$'H#$1-$1%/-%-/4'$%H(#1/'$1%$'("/'+%)*%
1/$#H/#$'%/-%/4'%&MH(#1/'$%78'
R
.

d
E%"*+%8'!-MH-6"H/-$%H(#1/'$%7!-8'
e
.
d
E%-6%*)/$-I'*"1'%7\4-#%
'/% "(C=% >??>A% B'$()*I#'//'% '/% "(C=% >??DEC% 0*% N"$/)H#("$=% /4'% +-#3('% H#3"*'%
XaB7NKE
f
_
>
!-
>
8'
D
.
R
7&g/
f
E
h
%1J1/'5%4"1%3''*%)*:'1/)I"/'+%"1%5-+'(%6-$%/4'%$'"H/):)/J%-6%/4'%
*)/$-I'*"1'% &
c
%H(#1/'$%7\4"*I%'/%"(C=%>??>A%\4"*I%;%a-(5=%>??fA%\#-%'/%"(C=%>??fEA%/4'%
H-5N('O%1#1/")*1%/'$5)*"(%()I"*+%1#31/)/#/)-*%2)/4%$'/'*/)-*%-6%/4'%!-
>
8'
D


f
M.E
D

h
M.E
>
%H-$'%
1/$#H/#$'%"*+%$'"$$"*I'5'*/%/-%/4'%!-
>
8'
D

>
M.E
>

f
M.E
D

D
M.E%/-N-(-IJ%-6%/4'%*)/$-I'*"1'%&
c
%
H(#1/'$% 7&'/'$1% '/% "(C=% @ddeA% !"J'$% '/% "(C=% @dddE%#N-*%$'"H/)-*%2)/4%H'$/")*%*#H('-N4)('1C%
i)1/)*H/%N$-H'11'1%6-$%/4'%H-*:'$1)-*%-6%+-#3('%H#3"*'1%/-%&
c
M/JN'%H(#1/'$1%"$'%+-H#5'*/'+=%
"66-$+)*I% /4'% N$-+#H/1% ^XaB7NKE

f
_
>
!-
>
8'
D
.
d
7.jE
>
`
fM
% 7\4"*I% ;% a-(5=% >??hE=%
^XaB7NKE
f
_
>
!-
>
8'
D
.
d
7.aE
>
`
fM
%7B'$()*I#'//'%;%a-(5=%>??DE=%^XaB7NKE
f

_
>
!-
>
8'
D
.
R
7P!'E
f
`
fM
%
7\4"*I% ;% a-(5=% >??hE=% ^XaB7NKE
f
_
>
!-
>
8'
D
.
e
7P!'E
h
`
>M
%7\4"*I%;%a-(5=%>??hE=%
^XaB7NKE
f

_
>
!-
>
8'
D
.
d
7PaE
>
`
fM
%7a(":)*Q"%'/%"(C=%>??eE=%^XaB7NKE
f
_
>
!-
>
8'
D
.
d
7P!'E
>
7a
>
PE`
fM
%
7a(":)*Q"% '/% "(C=% >??eE=% ^YXaB7NKE

f
_
>
!-
>
8'
D
.
d

>
MPE]
>
`
kM
%"*+%^XaB7NKE
f
_
>
!-
>
8'
D
.
R
s7saE
>
`
fM
%

7s% `%.=% .'E% )*%24)H4%as
M
%)1%"%/'$5)*"(%()I"*+%"*+%s
>M
%)1%"%µ
>
M3$)+I)*I% "/-5% )*%/4'% H-$'%
7a(":)*Q"%'/%"(C=%>??eEC%S4'%$':'$1'%/$"*16-$5"/)-*%-6%"%&
c
M/JN'%H(#1/'$%/-%"*%'+I'M3$)+I'+%
+-#3('%H#3"*'%4"1%3''*%+'5-*1/$"/'+%3J%/4'%$'"H/)-*%-6%^XaB7NKE
f
_
>
!-
>
8'
D
.
R
7P!'E
f
`
fM
%2)/4%
!'
f
.)Z%/-%"66-$+%^XaB7NKE
f
_

>
!-
>
8'
D
.
R
Z
h
`
>M
%7Z%`%,(
M
=%B$
M
E%7\4"*I%;%a-(5=%>??hEC%
0*% 3)-5)5'/)H% $'1'"$H4=% 5"*J% 6'2'$% 4'/'$-5'/"(% !8'
f
.
h
%H#3"*'M/JN'%H(#1/'$1%4":'%3''*%
1J*/4'1)K'+% 2)/4% :"*"+)#5% -$% /#*I1/'*% /4"*% 2)/4% 5-(J3+'*#5% 3'H"#1'% -6% /4'% 2'((M
'1/"3()14'+%1/$#H/#$"(%$'("/)-*14)N%-6%/4'%("//'$%/-%/4'%5-(J3+'*#5%H $+)*"/)-*%#*)/%)*%/4'%
*)/$-I'*"1'%!-8'MN$-/')*%7^''%;%a-(5=%>??fA%^''%;%a-(5=%>??hEC%F%1/$#H/#$"(%$'("/)-*14)N%
"NN'"$1%/-%'O)1/%3'/2''*%l8'
f
.
h
%H(#1/'$1%"*+%/4'%:"*"+)#5%1)/'%)*%l8'MN$-/')*1%7g"+J=%@ddDA%
g"+J=%>??fEC%8"$%6'2'$%:"*"+)#5%/4"*%5-(J3+'*#5%1)*I('%H#3"*'1%7.,E%H(#1/'$1=%H-*/")*)*I%

/4'% Xl8'
f

f
M.E
h
_% H-$'% -6% )+'"()K'+% /$)I-*"(% 1J55'/$J=% 4":'% 3''*% N$'N"$'+% 1)*H'% /4')$%
)*H'N/)-*%)*%@dRDM@dRe%7p-:"H1%;%a-(5=%@dRDA%p-:"H1%;%a-(5=%@dReA%p-:"H1%;%a-(5=%@dReE=%
"*+%/4'%6)$1/%"*+%-*(J%'O"5N('1%-6%:"*"+)#5%'+I'M3$)+I'+%+-#3('%H#3"*'1%7gBi,E=%2)/4%
/4'%H-$'%Xl
>
8'
D
.7Ǎ
f
M.E
D

h
M.E
>
_%-6%)+'"()K'+%H'*/$-1J55'/$J=%2'$'%-3/")*'+%)*%>??>%7\4"*I%'/%
"(C=% >??>EC% S4'% /2-% H(#1/'$% /JN'1% 5"J% 3'% I'*'$"()K'+% "1% ^XaB7NK
j
E
f
_l8'
f
.
h

Z
f
`
z
"*+%
^XaB7NK
j
E
f
_
>
l
>
8'
D
.
R
Z
h
`
z
-6% :"$)"3('% -O)+"/)-*% (':'(% z 2)/4% +):'$1'% 1H-$N)-*"/'% ()I"*+1%
74J+$-/$)17NJ$"K-(J(E3-$"/'% -$% /$)17NJ$"K-(J(E5'/4"*'1#(6-*"/'E% 3-#*+% /-% /4'% -H/"4'+$"(%
4'/'$-5'/"(%1)/'%"*+%()I"*+1% Z%7Z%`%N4-1N4)*'=%/4)-("/'=% -$%4"()+'E%"/%/4'%/'/$"4'+$"(%)$-*%
1)/'1C% S4'1'% 5"//'$1% "$'% 3'1/% N#$1#'+% 2)/4% H(#1/'$1% )*% 24)H4% XaB7NK
j
E
f
_
M

%)1%H-*1/"*/=%
6"H)()/"/)*I%/4'%)1-("/)-*%-6%H(#1/'$1%-6%')/4'$%4'/'$-5'/"(%2)/4%/4'%1"5'%H4"$I'%zC%0*6"H/=%/4'%
/$)17NJ$"K-(J(E3-$"/'% ()I"*+% H-*6-$51% /-% /4'% /$)I-*"(% 1J55'/$J% -6% /4'% .,% H-$'% "*+% )*%
1J*/4'1)1%I'*'$"((J%"66-$+1%.,1%2)/4%z `%M>%"*+%gBi,1%2)/4%z%`%Mf%-$%Mh%)*%1N'H)'1%H"$$J)*I%
5-*-"*)-*)H%()I"*+1%Z%78-5)/H4':%'/%"(C=%>??>A%a"#1'$%'/%"(C=%>??>A%\4"*I%;%a-(5=%>??fA%\#-%
'/%"(C=%>??fA%B'$()*I#'//'%'/%"(C=%>??DA%&'1":'*/-%'/%"(C=%>??eEC%%
j'H'*/(J=%"%1'$)'1%-6%1)*I('%H#3"*'%"*+%'+I'M3$)+I'+%+-#3('%H#3"*'%H(#1/'$1%H-*/")*)*I%/4'%
H-$'1%Xl8'
f

f
M.E
h
_
>q
%"*+%Xl
>
8'
D

f
M.E
D

h
M.E
>
_
>q
%4":'%3''*%N$'N"$'+%7.H-//%;%a-(5=%>??RE%3J%

()I"*+% 1#31/)/#/)-*% -6% /4'% N4-1N4)*'% H(#1/'$1% ^XaB7NKE
f
_l8'
f
.
h
7&g/
f
E
f
`
q
%"*+%
XaB7NKE
f
_
>
l
>
8'
D
.
R
7&g/
f
E
h
C% S4'% 1)*I('% H#3"*'1% ^XaB7NKE
f
_l8'

f
.
h
^
f
`
>M
%"*+%+-#3('%H#3"*'1%
^XaB7NKE
f
_l
>
8'
D
.
R
Z
h
`
hM
%7Z%`%8=%c
f
=%,c=%&4.E%"$'%14-2*%3J%ZM$"J%1/$#H/#$'1%/-%4":'%/$)I-*"(%
1J55'/$J% "*+% H'*/$-1J55'/$J=% $'1N'H/):'(JC% .)*I('% H#3"*'1% 6-$5% /4'% /4$''M5'53'$%
'('H/$-*%/$"*16'$%1'$)'1%^XaB7NKE
f
_l8'
f
.
h

Z
f
`
fM=>M=@M
C%S4'%()I"*+%+'N'*+'*H'%-6%$'+-O%N-/'*/)"(1%
"*+% '('H/$-*% +)1/$)3#/)-*% )*% H(#1/'$% H-$'1% "1% 1'*1'+% 3J%
ke
8'% )1-5'$% 14)6/1% 7DžE% 4":'% 3''*%
+'/'$5)*'+%7.H-//%;%a-(5=%>??REC%
Biomimetic Applications of Metal Systems Supported by Scorpionates

407
gO"5N('1% -6%<8'
f
.
h
%H(#1/'$1=%*'"$(J%"((%)*%/4'%6-$5%-6%/#*I1/'*M3$)+I'+%+-#3('%H#3"*'1=%
2'$'% N$'N"$'+% *'"$(J% 1)5#(/"*'-#1(J% 2)/4% 5-(J3+'*#5% H-*/")*)*I% H(#1/'$1% )*% /4'% '"$(J%
+':'(-N5'*/%-6%!y8'y.%H(#1/'$%H4'5)1/$J%7<-(66%'/%"(C=%@dR?A%F$51/$-*I%'/%"(C=%@dR>A%&"('$5-%
'/% "(C=% @dR>EC% 8'2% -/4'$1% 4":'% 3''*% N$'N"$'+% 1)*H'% /4"/% /)5'% 7,-#H-#:"*)1% '/% "(C=% @dd>A%
j"'3)I'$% '/%"(C=% @ddeEC%S4'%1/$#H/#$'1% -6%/#*I1/'*y)$-*y1#(6#$%H(#1/'$1% 4":'%3''*% 'ON(-$'+%
#1)*I%$'"H/)-*1%3"1'+%-*%^XaB7NK
!'=!'
E
f
_<.
f
`
M
%"1%N$'H#$1-$=%24)H4%$'"H/1%2)/4%8',(

>
=%c".g/%
"*+% .% "66-$+)*I% /4'% H#3"*'% H(#1/'$% ^XaB7NK
!'=!'
E
f
_<8'
f
.
h
,(
f
`
M
=% 24)H4% 2)/4% c".g/% )1%
H-*:'$/'+% /-% ^XaB7NK
!'=!'
E
f
_<8'
f
.
h
7.g/E
f
`
M
C% S$'"/5'*/% -6% ^XaB7NK
!'=!'
E

f
_<8'
f
.
h
,(
f
`
M
%2)/4%
g/
f
&%J)'(+1%/4'%'+I'M3$)+I'+%+-#3('%XaB7NK
!'=!'
E
f
_
>
<
>
8'
D
.
R
7&g/
f
E
h
%2)/4%/4'%X<
>

8'
D
7z
f
M.E
D
7z
h
M
.E
>
_%H-$'C%S4'%H#3"*'%H(#1/'$%^XaB7NK
!'=!'
E
f
_<8'
f
.
h
,(
f
E`
M
%$'"H/1%"(1-%2)/4%"*%'OH'11%-6%g/
f
&=%
Ba
h
M
%"*+%a.

M
%('"+)*I%"%5)O/#$'%-6%N$-+#H/1=%6$-5%24)H4%
^XaB7NK
!'=!'
E
f
_
>
<
>
8'
k
.
d
c"7.aE7!',cE`
fM
%2"1%)+'*/)6)'+C%S4)1%H(#1/'$=%"1%H(-1'(J%$'("/'+%
^XaB7NKE
f
_
>
!-
>
8'
D
.
d
7.aE
>
`

fM
=% 'O4)3)/1% "% H-$'% /-N-(-IJ% X<
>
8'
k
c"7Ǎ
>
M.E
>

f
M.E
D

D
M.E_% :'$J%
1)5)("$%/-%/4'%&
c
%H(#1/'$%-6%*)/$-I'*"1'%7a-*I%'/%"(C=%>??kEC%
3.3.2 Hydrogenase and related synthetic models
aJ+$-I'*"1'1% H-5N$)1'% "% 6#*+"5'*/"(% I$-#N% -6% 3"H/'$)"(% '*KJ5'1% /4"/% H"/"(JK'% /4'%
$':'$1)3('%-O)+"/)-*%-6%+)4J+$-I'*%/-%N$-/-*1%)*%"'$-3)H%"*+%"*"'$-3)H%5)H$ $I"*)151%"*+=%
/4#1=%N("J%"%Q'J%$-('%)*%5-('H#("$%3)-'*'$I'/)H1%78-*/'H)(("M,"5N1%;%j"I1+"('=%@dddA%F+"51%
;%./)'6'(=%>???A%!"/)"1%'/%"(C=%>??@A%,"$'N-%'/%"(C=%>??>EC%S2-%H("11'1%-6%4J+$-I'*"1'1=%X8'_M
-*(J%a
>
"1'1%7&"*+'J%'/%"(C=%>??RE%"*+%Xc)8'_%a
>
"1'1%7a)I#H4)%'/%"(C=%@dddE=%4":'%3''*%1/#+)'+%
2)+'(J=% '"H4% H-*/")*)*I% /4')$% 5'/"(1% )*% "% 4)I4% 1#(6#$% +'*1)/J% '*:)$-*5'*/C% S4'% ZM$"J%

H$J1/"((-I$"N4)H% 1/#+)'1% -6% /4'% "H/):'M1)/'% 1/$#H/#$'% -6% Xc)8'_% a
>
"1'1% )1-("/'+% 6$-5%
Desulfovibrio gigas=% Desulfovibrio lulgaris=% Desulfovibrio fructosovorans=% "*+% Desulfovibrio
desulfuricans FS,,>eeeh%)*%H-53)*"/)-*%2)/4%)*6$"$'+%1N'H/$-1H-NJ%4":'%$':'"('+%"*%"H/):'%
1)/'%H-5N$)1'+%-6%"%4'/'$-3)5'/"(()H%7.HJ1E
>
c)7ǍM.HJ1E
>
7ǍMZE8'7,PE7,cE
>
%7Z%`%P
>M
=%aP
>
M
=%Pa
M
E%
H(#1/'$%7l-(3'+"%'/%"(C=%@ddkA%j-#11'/%'/%"(C=%@ddRA%n"$H)*%'/%"(C=%@dddA%PI"/"%'/%"(C=%>??>A%,4)-#%
;%^)"2=%>??RE%78)IC%@D"EC%S4'%3$)+I)*I%()I"*+%Z%2"1%N$-N-1'+%/-%3'%"*%-O)+'=%4J+$-O)+'=%-$%
4J+$-N'$-O)+'%)*%/4'%-O)+)K'+%1/"/'%"*+%2"1%6-#*+%/-%3'%"31'*/%)*%/4'%$'+#H'+%1/"/'C%
%
%
8)IC%@DC%"E%j'N$'1'*/"/)-*%-6%/4'%"H/):'%1)/'%)*%/4'%Xc)8'_%4J+$-I'*"1'%'O/$"H/'+%6$-5%
Desulfovibrio gigas%14-2)*I%/4'%:"H"*/%H $+)*"/)-*%1)/'%7FE%"*+%/4'%"++)/)-*"(%3$)+I)*I%-O-%
-$%4J+$-O-%()I"*+%7ZE%N$'1'*/%-*(J%)*%/4'%-O)+)K'+%7)*"H/):'E%6-$5%-6%/4'%'*KJ5'A%3E%
1/$#H/#$'%-6%/4'%3-$"/$"*'%XYB7/)5
/B#
E

f
]8'7,PE
>
_C%
S4'1'% '*KJ5'1%4":'% 3'H-5'% 'OH'(('*/%/"$I'/1% 2)/4)*%3)-5)5'/)H%H4'5)1/$JC% !-+'(()*I%-6%
4J+$-I'*"1'% '*KJ5'1% $'L#)$'1% /4'% '66)H)'*/% 1J*/4'1)1% -6% 4"(6M1"*+2)H4% H-5N('O'1% -6% /4'%
6-$5%XaB7/)5
j
E
f
_c)Z%-$%Xa
>
B7/)5
j
E
>
_c)ZC%S4'%H4'5)1/$J%-6%*)Q'(%)1%+$):'*%3J%/4'%6-$5"/)-*%
-6%3)1M()I"*+%H-5N('O'1%1#H4%"1%XaB7/)5
j
E
f
_
>
c)%7n"$*'$%'/%"(C=%>??fA%.'*+"%'/%"(C=%>??DE%"*+%
Biomimetic Based Applications

408
Xa
>
B7/)5

j
E
>
_
>
c)%7F(:"$'K% '/%"(C=%>??@A% F(:"$'K%'/%"(C=% >??hEC%S4'% Xa
>
B7/)5
j
E
>
_
>
c)%H-5N('O'1=%
4":)*I% Xc).
h
a
>
_% H-$'1% "*+% 1()I4/(J% +)1/-$/'+% -H/"4'+$"(% I'-5'/$)'1% $'1#(/)*I% 6$-5% /4'%
#*'ON'H/'+% N$'1'*H'% -6% /2-% c)
{
ayB% )*/'$"H/)-*1=% H-*1/)/#/'% #*N$'H'+'*/'+% 1/$#H/#$"(%
5)5)H1% /4"/% $'1'53('% /4'% *)HQ'(% H $+)*"/)-*% '*:)$-*5'*/% )*% /4'% "H/):'% 6-$5% -6% Xc)8'_%
4J+$-I'*"1'1C% <)/4% XaB7/)5
!'
E
f
_
>
c)% )/% )1% N-11)3('% /-% -3/")*% /4'% -O)+)1'+% c)7000E% 1N'H)'1%

^XaB7/)5
!'
E
f
_
>
c)`
q
%"(3')/%)*%:'$J%(-2%J)'(+C%BJ%H-*/$"1/=%"%c)7000E%1N'H)'1%4"1%*-/%3''*%
)1-("/'+%6$-5%1/#+)'1%-6%/4'%"*"(-I-#1%Xa
>
B7/)5
j
E
>
_
>
c)%H-5N('O%7F(:"$'K%'/%"(C=%>??@EC%%
S4'% #1'% -6% "% 1/"$/)*I% 5"/'$)"(% H-*/")*)*I% "% H4'("/)*I% +)N4-1N4)*'% 1#H4% "1% @=>M
3)17+)N4'*J(N4-1N4)*-E'/4"*'% 7+NN'E% 5"J% N$':'*/% /4'% "++)/)-*% -6% "% 1'H-*+% XaB7/)5
j
E
f
_
M
%
I$-#N% /-% *)HQ'(% "*+% N("#1)3(J% I'*'$"/'% #1'6#(% H-5N('O'1% 1#H4% "1% XaB7/)5
j
E
f

_c)Z% -$%
Xa
>
B7/)5
j
E
>
_c)Z=%"((%24)('%N$'1'$:)*I%/4'%$'L#)$'+%1-6/%+-*-$%()I"*+%1'/%"$-#*+%/4'%5'/"(%
H'*/'$C%j'H'*/(J=%#1)*I%*)HQ'(%N4-1N4)*'%H-5N('O'1%)/%2"1%N-11)3('%/-%-3/")*%/4'%1N'H)'1%XN
f
M
a=.=.MaB7/)5
S-(
E
f
_c)7+NN'E,(=%XaB7/)5
S-(
E
f
_c)7cPE%"*+%XN
f
Ma=.=.Ma
>
B7/)5
!'
E
>
_c)7&&4
f
E7cPE%

7F(:"$'K%'/%"(C=%>??hA%!"66'//%'/%"(C=%>??eEC%
S4'% 1)5N('% H4'5)1/$J% -6% )$-*% )1% "(1-% +$):'*% 3J% /4'% 6-$5"/)-*% -6% 3)1M()I"*+% 1N'H)'1%
XaB7/)5
!'
E
f
_
>
8'% 7.'*+"% '/% "(C=% >??DEC% F(/4-#I4% XaB7/)5
!'
E
f
_
M
%N$-+#H'1%"*%-H/"4'+$"(%.
D
8'%
1N'H)'1% XN
f
M.=.=.MaB7/)5
!'
E
f
_
>
8'% 7.'*+"% '/% "(C=% >??DE=% /4'% XaB7/)5
&4
E
f
_

M
%()I"*+%I'*'$"/'+%"%
+)66'$'*/% )1-5'$% *"5'(J% XN
f
Ma=.=.MaB7/)5
&4
E
f
_
>
8'% 7p)53()*% '/% "(C=% >??@EC% BJ% "(/'$)*I% /4'%
1/-)H4)-5'/$J% "*+% $'"H/)-*% H-*+)/)-*1% )/% 2"1% N-11)3('% /-% N$-+#H'% 4"(6% 1"*+2)H4%
XaB7/)5
!'
E
f
_8',(%H-5N('O'1%"*+%H4(-$-%3$)+I'+%^XaB7/)5
!'
E
f
_8'7ǍM,(E`
>
%+)5'$1%-6%)$-*%7.'*+"%
'/%"(C=%>??DEC%S4'%)$-*%H'*/$'1%)*%4J+$-I'*"1'%"$'%-$I"*-5'/"(()H%)*%*"/#$'=%H-*/")*)*I%8'M,{P%
5-)'/)'1C%F(/4-#I4%H"$3-*J(%H-5N('O'1%-6%5"*I"*'1'%H"*%3'%N$-+#H'+%7B")('J%'/%"(C=%>??fE%"1%
J'/%2'%4":'%3''*%#*"3('%/-%+)$'H/(J%"*+%1)5N(J%N$-+#H'%/4'%"*"(-I-#1%)$-*%H-5N('O'1C%&"$Q)*%
et al.%#1'+%"%H)$H#)/-#1%$-#/'%/-%/4'1'%1N'H)'1=% 24)H4%N"11% /4$-#I4% "%3-$"/$"*'% XY
N
h
B=.=.m=.W-

B7/)5
/B#
E
f
]_8'7,PE
>
%1N'H)'1%78)IC%@D3EC%S4'%5-('H#("$% 1/$#H/#$'% -6% XY
N
h
B=.=.m=.W-
B7/)5
/B#
E
f
]_8'7,PE
>
%4"1%3''*%+'/'$5)*'+%3J%ZM$"J%+)66$"H/)-*=% 24)H4% H('"$(J% $':'"(1% /4'%
N$'1'*H'% -6% "*% 8'oBZ
f
% VM)*/'$"H/)-*C% .)I*)6)H"*/(J=% XY
N
h
B=.=.m=.W-B7/)5
/B#
E
f
]_8'7,PE
>
%'O4)3)/1%
*-:'(%$'"H/):)/J%/-2"$+1%"%:"$)'/J%-6%$'"I'*/1%/4"/%$'1#(/1%)*%'$"+)H"/)-*%-6%/4'%8'MB%3-*+%:)"%"%

6-$5"(% @=>M"++)/)-*% N$-H'11% "*+% /4'% 6-$5"/)-*% -6% BM6#*H/)-*"()K'+%
/$)175'$H"N/-)5)+"K-(J(E3-$"/'%+'$):"/):'1=%XZB7/)5
/B#
E
f
_8'[%78)I#'$-"%'/%"(C=%>??DEC%%
0/%)1%*-/'+%/4"/%/4'%$'N-$/1%I'*'$"/'+%24)H4%$'("/'+%/-%4J+$-I'*"1'%H4'5)1/$J%"$'%/4#1%6"$%
6$"I5'*/'+C% % a-2':'$=% )6% /4'J% H"*% 3'% ()*Q'+% "% :)"3('% 5-+'(% -6% 4J+$-I'*"1'% H-#(+%
N-/'*/)"((J% 3'% I'*'$"/'+C% 8-$% 'O"5N('=% 1N'H)'1% 1#H4% "1% XN
f
Ma=.=.MaB7/)5
S-(
E
f
_c)7+NN'E,(%
H-*/")*% "% 5'/"(% 73-$-E4J+$)+'% )*/'$"H/)-*% 7F(:"$'K% '/% "(C=% >??@A% F(:"$'K% '/% "(C=% >??hEC%
8#$/4'$5-$'%/4'%4J+$)+'%H"*%3'%)*+#H'+%/-%('":'%/4'%3-$-*%"*+%"%5'/"(%5'+)"/'+%4J+$)+'%
/$"*16'$%H"*%3'%)*)/)"/'+C%F1%2)/4%5#H4%3)-M5)5'/)H%H4'5)1/$J=%5-+'(()*I%$'"H/)-*1%N"$"(('(%
/4'% $'1N'H/):'% '*KJ5'1% /-% "% N-)*/% 7'CIC% $'N("H'5'*/% -6% cFi
q
%3J%3'*KJ(*)H-/)*"5)+'%
H4(-$)+'%)*%K)*H%"(H-4-(%+'4J+$-I'*"1'%1/#+)'1E%"*+%/4'%5"**'$%)*%24)H4%/4'%'('H/$-*1%"$'%
5"*"I'+%)*%/4'%4J+$-I'*"1'%5-+'(%$'"H/)-*%)1%#*()Q'(J%/-%5)5)H%/4"/%-6%/4'%'*KJ5'%"1%/4'$'%
)1%*-%N"/42"J%6-$%/4'5%/-%3'%1'L#'1/'$'+C%0*%/4)1%H"1'%)/%)1%()Q'(J%/4"/%/4'J%2)((%3'%1/-$'+%)*%"%
3-*+%1#H4%"1%/4'%BMa%3-*+%7j'I()*1Q)%;%.N)H'$=%>??dEC%
4. Acknowledgments
S4)1% 2-$Q% 2"1% 6)*"*H)"((J% 1#NN-$/'+% 3J% !)*)1/'$-% +'((U01/$#K)-*'% +'((Uv*):'$1)/|% '% +'(("%
j)H'$H"%7&j0c%>??eRg<pdBEC%<'%%"$'%I$"/'6#(%/-%,0j,!.B%7,-*1-$K)-%0*/'$#*):'$1)/"$)-%+)%
j)H'$H"%)*%,4)5)H"%+')%!'/"(()%*')%.)1/'5)%B)-(-I)H)EC%
Biomimetic Applications of Metal Systems Supported by Scorpionates


409
5. References
F+"51=%!C<C<C%;%./)'6'(=%gC0C%7>???EC%P$I"*-5'/"(()H%)$-*b%/4'%Q'J%/-%3)-(-I)H"(%4J+$-I'*%
5'/"3-()15C%Curr. Opin. Chem. Biol.=%h=%>@hM>>?C%
F(16"11'$=%jC=%j#6=%!C=%S$-6)5'*Q-=%.C%;%l"4$'*Q"5N=%aC%7@ddfEC%F*%^
f
\*Pa%H-5N('O%"1%"%
6#*H/)-*"(%5-+'(%-6%/4'%'*KJ5'%H"$3-*)H%"*4J+$"1'C%Chem. Ber.=%@>D=%e?fMe@?C%
F(16"11'$=% jC=% S$-6)5'*Q-=% .C=% ^ *'J=% FC=% &"$Q)*=% nC% ;% l"4$'*Q"5N=% aC% 7@dd@EC% F%
5-*-*#H('"$% K)*H% 4J+$-O)+'% H-5N('O% 1/"3)()K'+% 3J% "% 4)I4(J% 1#31/)/#/'+%
/$)17NJ$"K-(J(E4J+$-3-$"/-%()I"*+b%"*"(-I)'1%2)/4%/4'%'*KJ5'%H"$3-*)H%"*4J+$"1'C%
Inorg. Chem.=%f?=%h?dRMh@??C%
F(:"$'K=% aC!C=% p$"2)'H=% !C=% i-*-:"*M!'$Q'$/=% BCSC=% 8-#K)=% !C% ;% j"3)*-:)H4=% iC% 7>??@EC%
!-+'()*I%c)HQ'(%aJ+$-I'*"1'1b%.J*/4'1)1%"*+%./$#H/#$'%-6%"%i)1/-$/'+%PH/"4'+$"(%
,-5N('O%2)/4%"*%v*N$'H'+'*/'+%Xc).
h
a
>
_%,-$'C%Inorg. Chem.=%h?=%kefDMkefeC%
F(:"$'K=% aC!C=% S"*1Q)=% uC!C% ;% j"3)*-:)H4=% iC% 7>??hEC% &-(J75'$H"N/-)5)+"K-(J(E3-$"/'%
H4'5)1/$J% "*+% /4'%N$'+-5)*"*H'% -6% Nj
f
M.=.=a% -:'$% Nj
>
M.=.% -$% Nj
f
M.=.=.% H $+)*"/)-*%
5-+'1b%#*'ON'H/'+%6-$5"/)-*%-6%1L#"$'%NJ$"5)+"(%c)700E%H-5N('O'1C%Polyhedron=%>f=%
fdkMh?fC%

F*+$')*)=%,C=%B'$/)*)=%0C=%,":"(("$-=%nC=%a-(()+"J=%nC^C%;%S4-$*/-*=%uC!C%7>??REC%!'/"(%)-*1%)*%
3)-(-I)H"(% H"/"(J1)1b% 6$-5% '*KJ5'% +"/"3"1'1% /-% I'*'$"(% N$)*H)N('1C% J. Biol. Inorg.
Chem.=%@f=%@>?kM@>@RC%
F*/-*J#Q=% .ClC=% ./$"*I'=% jC<C=% ."2'$1=% nC=% g"+J=% jCjC% ;% a"1*")*=% .C.C% 7>??kEC% F/-5)H%
$'1-(#/)-*%1/$#H/#$'1%-6%$'1/)*IM1/"/'=%1#31/$"/'M%"*+%N$-+#H/MH-5N('O'+%,#M*)/$)/'%
$'+#H/"1'%N$-:)+'%)*1)I4/%)*/-%H"/"(J/)H%5'H4"*)15C%Proc. Natl. Acad. Sci. U. S. A.=%
@?>=%@>?h@M@>?hDC%
F$51/$-*I=% <CaC% ;% ^)NN"$+=% .CuC% 7@dRhEC% j':'$1)3('% N$-/-*"/)-*% -6% /4'% -O-% 3$)+I'% )*% "%
4'5'$J/4$)*% 5-+'(% H-5N-#*+C% .J*/4'1)1=%1/$#H/#$'=%"*+%N$-N'$/)'1%-6%7PM
4J+$-O-E3)17PM"H'/"/-E3)1X4J+$-/$)17@MNJ$"K-(J(E3-$"/-_+))$-*7000E%
X7aB7NKE
f
E8'7PaE7P
>
,,a
f
E
>
8'7aB7NKE
f
E
>
_
q
C%J. Am. Chem. Soc.=%@?D=%hDf>MhDffC%
F$51/$-*I=%<CaC=% !"1H4"$"Q=%&CpC%;% a-(5=%jCaC% 7@dR>EC%i-#3(J%3$)+I'+% +-#3('%H#3"*'1%
H-*/")*)*I% !8'
f
.
h

% H(#1/'$1C% .J*/4'1)1=% 1/$#H/#$'=% "*+% H-*:'$1)-*% /-% 1N)*ML#"$/'/%
1)*I('%H(#1/'$1%)*%1-(#/)-*C%J. Am. Chem. Soc.=%@?h=%hfefMhfRfC%
F$51/$-*I=% <CaC=% .N (=% FC=% &"N"'6/4J5)-#=% nC,C=% 8$"*Q'(=% jCBC% ;% ^)NN"$+=% .CuC% 7@dRhEC%
F11'53(J% "*+% H4"$"H/'$)K"/)-*% -6% "*% "HH#$"/'% 5-+'(% 6-$% /4'% +))$-*% H'*/'$% )*%
4'5'$J/4$)*C%J. Am. Chem. Soc.=%@?D=%fDkfMfDDeC%
F#(+=%iC.C%7>??DEC%Zinc Enzymes=%u-4*%<)('J%;% *1=%^/+C%
F:'$)((=%BCFC%7@ddDEC%i)11)5)("/-$J%*)/$)/'%"*+%*)/$)H%-O)+'%$'+#H/"1'1C%Chem. Rev.=%dD=%>dk@M
>dDhC%
B"+#$"=% iC% ;% l"4$'*Q"5N=% aC% 7>??>EC% &J$"K-(J(3-$"/'M\)*HMc#H('-3"1'M,-5N('O'1=% >b%
&$'N"$"/)-*1% "*+%./$#H/#$'1%-6% SN,#5=!'\*%"*+% SN&4=!'\*% ,-5N('O'1C% Inorg.
Chem.=%h@=%D?@fMD?@dC%
B"+#$"=%iC%;%l"4$'*Q"5N=%aC%7>??>EC%&J$"K-(J(3-$"/'M\)*HMc#H('-3"1'M,-5N('O'1=%fb%B"1'%
&")$)*I%./#+)'1C%Inorg. Chem.=%h@=%D?>?MD?>eC%
B")('J=% &CuC=% ^-$-*-Mn-*K"('1=% iCuC=% !H,-$5"HQ=% ,C=% &"$1-*1=% .C% ;% &$)H'=% !C% 7>??fEC%
S$)15'/4)5"K-(J(4J+$-3-$"/'%7S5E%H-5N('O'1%-6%$#/4'*)#5%"*+%5"*I"*'1'C%Inorg.
Chim. Acta=%fkh=%D@MDeC%
B"1#5"(()HQ=%^C=%i'B''$%n'-$I'=%.C=%j"*+"((=%iC<C=%a'+5"*=%BC=%a-+I1-*=%pCPC=%8#G)1"2"=%pC%
;% (-5-*=% gC0C% 7>??>EC% .N'H/$-1H-N)H% H-5N"$)1-*% -6% /4'% 6):'MH $+)*"/'%
Biomimetic Based Applications

410
X,#7.!'05E7aB7f=kM)&$
>
NKE
f
E_% 2)/4% /4'% 6-#$MH $+)*"/'% X,#7.,&4
f
E7aB7f=kM
)&$
>

NKE
f
E_b%'66'H/%-6%HC*C%)*H$'"1'%-*%"%3(#'%H-NN'$%/JN'%1)/'C%Inorg. Chim. Acta=%ffe=%
fkeMfDkC%
B'HQ=% FC=% <')3'$/=% BC% ;% B#$K("66=%cC%7>??@EC%!-*-"*)-*)H%c=c=PM1H-$N)-*"/'% ()I"*+1% "*+%
/4')$%)$-*700E%"*+%K)*H700E%H-5N('O'1b%5-+'(1%6-$%5-*-*#H('"$%"H/):'%1)/'1%-6%*-*M
4'5'%)$-*%-O)+"1'1%"*+%K)*H%'*KJ5'1C%Eur. J. Inorg. Chem.=%k>@Mk>eC%
B'*Q5)(=%BC=%u)=%!C%;%l"4$'*Q"5N=%aC%7>??hEC%B)17NJ$"K-(J(E7/4)-)5)+"K-(J(E3-$"/'%^)I"*+1b%
S4'%!)11)*I%!'53'$%)*%/4'%cfCCC.f%.H-$N)-*"/'%.'$)'1C%Inorg. Chem.=%hf=%R>@>MR>@hC%
B'$IL#)1/=%,C=%8)(('3''*=%SC=%!-$(-Q=%!C!C%;% &"$Q)*=%nC% 7>??fEC%&$-/-*"/)-*%"*+% j'"H/):)/J%
/-2"$+1% ,"$3-*% i)-O)+'% -6% /4'% !-*-*#H('"$% S'/$"4'+$"(% \)*H% "*+% ,-3"(/%
aJ+$-O)+'% ,-5N('O'1=% XSN
B#/=!'
_\*Pa% "*+% XSN
B#/=!'
_,-Pab% ,-5N"$)1-*% -6% /4'%
j'"H/):)/J% -6% /4'% !'/"(% aJ+$-O)+'% 8#*H/)-*% )*% .J*/4'/)H% F*"(-I#'1% -6% ,"$3-*)H%
F*4J+$"1'C%J. Am. Chem. Soc.=%@>k=%D@RdMD@ddC%
B'$IL#)1/=% ,C% ;% &"$Q)*=% nC% 7@dddEC% &$-/-*"/)-*% -6% /4'% aJ+$-O)+'% ^)I"*+% )*% "% .J*/4'/)H%
F*"(-I#'% -6% ,"$3-*)H% F*4J+$"1'=% XSN
B#/=!'
_\*Pab% 0*4)3)/)-*% -6% j'"H/):)/J%
S-2"$+1%,P
>
C%J. Am. Chem. Soc.=%@>@=%Df>>MDf>fC%
B'$IL#)1/=%,C=%./-$$)'=%aC=%p-#/H4'$=%^C=%B$)+I'2"/'$=%BC!C=%8$)'1*'$=%jCFC%;%&"$Q)*=%nC%7>???EC%
8"H/-$1%)*6(#'*H)*I%/4'%/4'$5-+J*"5)H1%-6%K)*H%"(Q-O)+'%6-$5"/)-*%3J%"(H-4-(J1)1%
-6% /4'% /'$5)*"(% 4J+$-O)+'% H-5N('O=% XSN
B#/=!'
_\*Pab% "*% 'ON'$)5'*/"(% "*+%

/4'-$'/)H"(% 1/#+J% $'(':"*/% /-% /4'% 5'H4"*)15% -6% "H/)-*% -6% ():'$% "(H-4-(%
+'4J+$-I'*"1'C%J. Am. Chem. Soc.=%@>>=%@>Dk@M@>DkRC%
B'$()*I#'//'=%,C&C%;%a-(5=%jCaC%7>??DEC%g+I'MB$)+I'+%!-
>
8'
D
.
R
%/-%&
c
MSJN'%!-
>
8'
D
.
d
%,(#1/'$%
,-*:'$1)-*b%./$#H/#$"(%8"/'%-6%/4'%F//"HQ)*I%.#(6)+'r.'('*)+'%c#H('-N4)('C%J. Am.
Chem. Soc.=%@>R=%@@ddfM@>???C%
B'$()*I#'//'=%,C&C=%!)J"G)=%SC=%\4"*I=%[C%;%a-(5=%jCaC%7>??DEC%&$'H#$1-$1%/-%,(#1/'$1%2)/4%/4'%
S-N-(-IJ%-6%/4'%&c%,(#1/'$%-6%c)/$-I'*"1'b%g+I'MB$)+I'+%i-#3('%,#3"*'%,(#1/'$1%
X7SNE
>
!-
>
8'
D
.
R
^

h
_
K
C%Inorg. Chem.=%hk=%@ddeM>??eC%
B'$/)*)=% 0C=% n$"J=% aCBC=% ./)'6'(=% gC0C% ;% l"('*/)*'=% uC.C% 7>??DEC% Biological Inorganic Chemistry:
Structure and Reactivity @'+; v*):'$1)/J%.H)'*H'%B Q1C%
B'$/)*)=% 0C=% ^#H4)*"/=% ,C% ;% &)HH)-()=% !C% 7>??@EC% &"$"5"I*'/)H% N$-3'1% )*% 5'/"((-N$-/')*1C%
Methods Enzymol.=%ffd=%f@hMfh?C%
B'$/)*)=%0C=%.)I'(=%FC%;%.)I'(=%aC%7>??@EC%Handbook on Metalloproteins=%,j,%&$'11C%
B$"*+=% vC=%j-53"H4=% !C=%.''3"H4'$=% uC% ;%l"4$'*Q"5N=%aC% 7>??@EC%8#*H/)-*"(% !-+'()*I% -6%
,-3"("5)*'M0*+'N'*+'*/%!'/4)-*)*'%.J*/4"1'%2)/4%&J$"K-(J(3-$"/'M\)*HMS4)-("/'%
,-5N('O'1C%Inorg. Chem.=%h?=%D@k@MD@keC%
B$)+I'2"/'$=%BC!C=%8)(('3''*=%SC=%8$)'1*'$=%jCFC%;%&"$Q)*=%nC%7>???EC%F%K)*H%/4)-("/'%1N'H)'1%
24)H4% 5)5)H1% "1N'H/1% -6% /4'% H4'5)1/$J% -6% /4'% F+"% $'N")$% N$-/')*% "*+% 5"/$)O%
5'/"((-N$-/')*"1'1b%/4'%1J*/4'1)1=%1/$#H/#$'%"*+%$'"H/):)/J%-6%/4'%/$)17>M5'$H"N/-M@M
N4'*J()5)+"K-(J(E4J+$-3-$"/-%H-5N('O%XS5
&4
_\*.&4C%Dalton=%hhdhMhhdDC%
B$)+I'2"/'$=% BC!C% ;% &"$Q)*=% nC% 7>???EC% ^'"+% &-)1-*)*I% "*+% /4'% 0*"H/):"/)-*% -6% kM
F5)*-(':#()*"/'% i'4J+$"/"1'% "1% !-+'('+% 3J% /4'% S$)17>M5'$H"N/-M@M
N4'*J()5)+"K-(J(E4J+$-3-$"/-%^'"+%,-5N('O=%YXS5
&4
_&3]X,(P
h
_C%J. Am. Chem. Soc.=%
@>>=%e@h?Me@h@C%
B$)+I'2"/'$=% BC!C% ;% &"$Q)*=% nC% 7>??@EC% F% K)*H% 4J+$-O)+'% H-5N('O% -6% $'(':"*H'% /-% kM
"5)*-(':#()*"/'% +'4J+$"/"1'b% S4'% 1J*/4'1)1=% 1/$#H/#$'% "*+% $'"H/):)/J% -6% /4'%
H-5N('O%XS5
&4

_\*PaC%Inorg. Chem. Commun.=%h=%@>DM@>dC%
Biomimetic Applications of Metal Systems Supported by Scorpionates

411
B$-53"H4'$=% aC% ;% l"4$'*Q"5N=% aC% 7>??hEC% &J$"K-(J(3-$"/'M\)*H% F(Q-O)+'% ,-5N('O'1C% fC%
FH)+MB"1'%j'"H/)-*1C%Inorg. Chem.=%hf=%D?khMD?D?C%
B$-*+)*-=%,CiC=%j-5"-=%!CuC=%!-#$"=%0C%;%!-#$"=%uCuCnC%7>??DEC%!-(J3+'*#5%"*+%/#*I1/'*%
'*KJ5'1b%/4'%O"*/4)*'%-O)+"1'%6"5)(JC%Curr. Opin. Chem. Biol.=%@?=%@?dM@@hC%
B$#H'=% !C0C% ;% P1/"K'21Q)=% FC&C&C% 7@defEC% n$-#N% 0B% 5'/"(% H4'5)1/$JC% 0C% &$'N"$"/)-*% "*+%
$'"H/)-*1% -6% /4'% H"$3-*J(74J+$-/$)NJ$"K-(M@MJ(3-$"/-EH-NN'$70E% H-5N('OC% J. Chem.
Soc., Dalton Trans.=%>hffM>hfDC%
B#$I'11=%BCpC%;%^-2'=%iCuC%7@ddDEC%!'H4"*)15%-6%!-(J3+'*#5%c)/$-I'*"1'C%Chem. Rev.=%dD=%
>dRfMf?@@C%
B#/('$=%FC%7@dddEC%!'H4"*)1/)H%H-*1)+'$"/)-*1%-6%/4'%:"*"+)#5%4"(-N'$-O)+"1'1C%Coord. Chem.
Rev.=%@Re=%@eMfkC%
,"(+'$-*'=% lC=% i-(+'$'$=% BC=% a"$/5"**=% aCMuC=% gH4*'$=% aC=% ^#H4)*"/=% ,C=% i'(% B)"*H-=% ,C=%
!"*I"*)=%.C%;%<'1'$=%vC%7>??kEC%S4'%H$J1/"(%1/$#H/#$'%-6%J'"1/%H-NN'$%/4)-*')*b%S4'%
1-(#/)-*%-6%"%(-*IM("1/)*I%'*)I5"C%Proc. Natl. Acad. Sci. U. S. A.=%@?>=%k@MkDC%
,"*/'$1=%nC<C%;%n)("$+)=%nC%7@ddfEC%g*I)*''$)*I%/JN'%@%H-NN'$%1)/'1%)*%N$-/')*1C%FEBS Lett.=%
f>k=%fdMhRC%
,"$'N-=%!C=%S)'$*'J=% iC^C=%B$-*+)*-=% ,CiC=%["*I=%SC,C=%&"5N(-*"=%FC=% S'(1'$=%uC=%!-#$"=%0C=%
!-#$"=%uCuCnC%;%a-665"*=%BC!C%7>??>EC%
@e
P%gciPj%i'/'H/)-*%-6%"% (:'*/Mi'$):'+%
c)M7PaOEM8'% B$)+I'% S4"/% 01% ^-1/% #N-*% FH/):"/)-*% -6% /4'% aJ+$-I'*"1'% 6$-5%
i'1#(6-:)3$)-%I)I"1C%J. Am. Chem. Soc.=%@>h=%>R@M>RDC%
,"$$)'$=%.C!C=%j#II)'$-=%,CgC=%S-(5"*=%<CBC%;%u"5'1-*=%nCBC%7@dd>EC%.J*/4'1)1%"*+%1/$#H/#$"(%
H4"$"H/'$)K"/)-*%-6%"%5-*-*#H('"$%H-NN'$%*)/$-1J(%H-5N('OC%J. Am. Chem. Soc.=%@@h=%
hh?eMhh?RC%
,4"*=%!CpC=%p)5=%uC%;%j''1=%iC,C%7@ddfEC%S4'%*)/$-I'*"1'%)$-*M5-(J3+'*#5MH-6"H/-$%"*+%&M

H(#1/'$%N")$b%>C>%Ct%$'1-(#/)-*%1/$#H/#$'1C%Science=%>D?=%ed>MedhC%
,4"#+4#$)=%&C%;%<)'I4"$+/=%pC%7>??@EC%&4'*-OJ(%$"+)H"(%H-5N('O'1C%Prog. Inorg. Chem.=%k?=%
@k@M>@DC%
,4'*=%&C=% j /=% iCgC=%,"5N-H4)"$-=% ,C=%8#G)1"2"=% pC% ;% (-5-*=% gC0C%7>??fEC% .N'H/$-1H-N)H%
"*+% g('H/$-*)H% ./$#H/#$'% ./#+)'1% -6% /4'% i)"5"I*'/)H% .)+'MP*% ,#
00
M.#N'$-O-%
,-5N('O% ,#7P
>
EXaB7fMjMkM)&$NKE
f
_C% F*/)6'$$-5"I*'/)H% ,-#N()*I% :'$1#1% ,-:"('*/%
i'(-H"()K"/)-*C%J. Am. Chem. Soc.=%@>k=%hDDMhehC%
,4)-#=%SCM<C%;%^)"2=%<CM8C%7>??REC%!-*-*#H('"$%c)HQ'(7000E%,-5N('O'1%Xc)
000
7PjE7&7,
D
a
f
MfM
.)!'
f
M>M.E
f
E_
M
%7j%`%!'=%&4E%,-*/")*)*I%/4'%S'$5)*"(%F(Q-O)+'%^)I"*+b%j'(':"*H'%/-%
/4'%c)HQ'(%.)/'%-6%PO)+)K'+M8-$5%Xc)8'_%aJ+$-I'*"1'1C%Inorg. Chem.=%he=%ed?RMed@fC%
,4$)1/)"*1'*=% uC=% i'"*=% iCjC% ;% .''6'(+/=% ^C,C% 7>??@EC% !'H4"*)1/)H% 6'"/#$'1% -6% /4'% !-M
H-*/")*)*I%*)/$-I'*"1'C%Annu. Rev. Plant Physiol. Plant Mol. Biol.=%k>=%>DdM>dkC%

,4#$H4)((=% !CjC=% i'B-'$=% BCnC=% j-/'(("=% 8CuC=% F3#% ."("4=% PC!C% ;% B$#H'=% !C0C% 7@dekEC%
i'/'$5)*"/)-*% -6% /4'% H$J1/"(% 1/$#H/#$'% "*+% 5-('H#("$% I'-5'/$J% -6% X4J+$-/$)17@M
NJ$"K-(J(E3-$"/-_H-NN'$70E% H"$3-*J(C% v*)L#'% 1/$#H/#$"(%)*:'1/)I"/)-*%-6%"% H-NN'$M
H"$3-*J(%()*Q"I'C%Inorg. Chem.=%@h=%>?k@M>?kDC%
,-('5"*=%uCgC%7@dd>EC% \)*H%&$-/')*1b%g*KJ5'1=%./-$"I'%&$-/')*1=%S$"*1H$)N/)-*% 8"H/-$1=%"*+%
j'N()H"/)-*%&$-/')*1C%Annual Review of Biochemistry=%D@=%RdeMdhDC%
,-(5"*=% &C!C=% 8$''5"*=% aC,C=% n#11=% uC!C=% !#$"/"=% !C=% c-$$)1=% lCFC=% j"514"2=% uCFC!C% ;%
l'*Q"/"NN"=%!C&C%7@deREC%ZM$"J%H$J1/"(%1/$#H/#$'%"*"(J1)1%-6%N("1/-HJ"*)*%"/%>Ce%t%
$'1-(#/)-*C%Nature=%>e>=%f@dMf>hC%
Biomimetic Based Applications

412
,-#H-#:"*)1=% iC=% F(MF45"+=% .CFC=% ."()6-I(-#=% FC=% &"N"'6/4J5)-#=% lC=% p-1/)Q"1=% FC% ;%
.)5-N-#(-1=% FC%7@dd>EC% .J*/4'1)1=%H4"$"H/'$)K"/)-*=% "*+%$'"H/):)/J% -6%*'2% H(#1/'$1%
/4"/%H-*/")*%/4'%X!8'
f
.
h
_%H-$'=%!%`%5-(J3+'*#5=%/#*I1/'*C%J. Am. Chem. Soc.=%@@h=%
>he>M>hR>C%
,$"*1=% iC,C=% .5''=% uCuC=% n")+"5"#1Q"1=% gC% ;% ["*I=% ^C%7>??hEC%S4'%,4'5)1/$J%"*+%
B)-H4'5)1/$J% -6% l"*"+)#5% "*+% /4'% B)-(-I)H"(% FH/):)/)'1% gO'$/'+% 3J% l"*"+)#5%
,-5N-#*+1C%Chem. Rev.=%@?h=%RhdMd?>C%
,#66=%!CgC=%!)(('$=%pC0C=%l"*%a-(+'=%pCgC%;%a'*+$)HQ1-*=%<CFC%7@ddREC%,$J1/"(%1/$#H/#$'%-6%"%
6#*H/)-*"(%#*)/%6$-5%PH/-N#1%4'5-HJ"*)*C%J. Mol. Biol.=%>eR=%RkkMRe?C%
,:'/Q-:)H=% !C=% B"//'*=% .CjC=% !-#3"$"Q)=% BC=% !#$$"J=% pC.C% ;% .N)HH)"=% ^C% 7>??@EC% ,-NN'$70E%
/$)17NJ$"K-(J(E5'/4"*'% H-5N('O'1% "*+% /4')$% $'"H/):)/J% /-2"$+1% +)-OJI'*C% Inorg.
Chim. Acta=%f>h=%@f@M@h?C%
,K'$*#1K'2)HK=% jC.C=% .4'"/1=% uCgC% ;% .N)$-=% SCnC% 7@dReEC% j'1-*"*H'% j"5"*% 1N'H/$"% "*+%
'OH)/"/)-*% N$-6)('% 6-$% 3)17"H'/"/-E3)174J+$-/$)NJ$"K-(J(3-$"/-E-O-+))$-*=% "%

4'5'$J/4$)*%"*"(-IC%Inorg. Chem.=%>D=%>?DfM>?DeC%
i'*% B(""#2'*=%SC% ;%,"*/'$1=% nC<C% 7@ddfEC%,$'"/)-*% -6%/JN'M@% "*+%/JN'M>% H-NN'$% 1)/'1%3J%
"++)/)-*%-6% 'O-I'*-#1%()I"*+1%/-% /4'%&1'#+-5-*"1%"'$#I)*-1"% "K#$)*%a)1@@en(J%
5#/"*/C%J. Am. Chem. Soc.=%@@k=%@@>@M@@>dC%
i'*%B(""#2'*=%SC=%a-)/)*Q=%,C<C=%,"*/'$1=%nC<C=%a"*=% uC=%^-'4$=%SC!C%;%."*+'$1M^-'4$=%uC%
7@ddfEC% j'1-*"*H'% j"5"*% 1N'H/$-1H-NJ%-6%/4'%"K#$)*%a)1@@en(J%5#/"*/C%
0*/'$H-*:'$1)-*% -6% /JN'% @% "*+% /JN'% >% H-NN'$% 1)/'1% /4$-#I4% 'O-I'*-#1% ()I"*+1C%
Biochemistry=%f>=%@>hkkM@>hDhC%
i'1$-H4'$1=%&CuC=%,#//1=%jC<C=%j)H'=%&CpC=%n-(+'*=%!C^C=%n$"4"5=%uCBC=%B"$H("J=%SC!C%;%,-$+'1=%
FC<C% 7@dddEC% ,4"$"H/'$)1/)H1% -6% 8):'M, $+)*"/'% c)HQ'(M,J1/')*'% ,'*/'$1C% Inorg.
Chem.=%fR=%kDd?MkDdhC%
i)"1=% aClCjC% ;% 8)"*H4)*)=% !C% 7>??eEC% 8(#-$)*"/'+% S$)17&J$"K-(J(EB-$"/'1% "*+% .)(:'$70E%
,-5N('O'1%-6%n$-#N%@h%^)I"*+1C%Comments Inorg. Chem.=%>R=%efMd>C%
i-2()*I=% ,C% ;% &"$Q)*=% nC% 7@ddDEC% g("3-$"/)-*% -6% /4'% 3)17NJ$"K-(J(E4J+$-3-$"/-% ()I"*+%
XBN
B#/=&$)
_%)*/-%/4'%ccP%+-*-$%()I"*+=%X7!'PEBN
B#/=&$)
_b%1/$#H/#$'%H4"$"H/'$)K"/)-*%-6%
"%H-5N('O%)*%24)H4%/4'% X7!'PEBN
B#/=&$)
_%()I"*+%5-+'(1%/4'%3)*+)*I%-6% K)*H%/-% /4'%
N'N/)+'%3"HQ3-*'%)*%/4'$5-(J1)*C%Polyhedron=%@k=%>hDfM>hDkC%
i#$('J=%jC=% ,4'*=%^C=%^)5=% ^C<C=%!"/4'21=%8C.C% ;%i":)+1-*=%lC^C% 7@ddfEC%,$J1/"(% 1/$#H/#$'%
"*"(J1)1%-6%"5)HJ"*)*%"*+%"N-"5)HJ"*)*%6$-5%&"$"H-HH#1%+'*)/$)6)H"*1%"/%>C?%t%"*+%
@CR%t%$'1-(#/)-*C%Protein Science=%>=%efdMek>C%
g"+J=% jCjC% 7@ddDEC%./$#H/#$'M6#*H/)-*% $'("/)-*14)N1%-6% "(/'$*"/):'% *)/$-I'*"1'1C%Chem. Rev.=%
dD=%f?@fMf?f?C%
g"+J=% jCjC% 7>??fEC% ,#$$'*/% 1/"/#1% -6% 1/$#H/#$'% 6#*H/)-*% $'("/)-*14)N1% -6% :"*"+)#5%
*)/$-I'*"1'C%Coord. Chem. Rev.=%>fe=%>fMf?C%

g+'(5"**=% 8CSC% 7>??@EC% l'$1"/)('% 1H-$N)-*"/'1M*'2% +':'(-N5'*/1% )*% /4'% H $+)*"/)-*%
H4'5)1/$J%-6%NJ$"K-(J(3-$"/'%()I"*+1C%Angew. Chem. Int. Ed. Engl.=%h?=%@DkDM@DD?C%
g)*1('=%PC=%S'KH"*=%8CFC=%F*+$"+'=%.C^CFC=%.H45)+=%BC=%[-14)+"=%!C=%a-2"$+=%uCBC%;%j''1=%iC,C%
7>??>EC% c)/$-I'*"1'% !-8'MN$-/')*% "/% @C@D% t% $'1-(#/)-*b% F% H'*/$"(% ()I"*+% )*% /4'%
8'!-MH-6"H/-$C%Science=%>de=%@DdDM@e??C%
g*'5"$Q=% uCaC=% , *'J=%uCuCFC=% <"*I=% uCMuC% ;%a-(5=% jCaC% 7>??hEC% .J*/4'/)H%F*"(-I#'1% "*+%
j'"H/)-*% .J1/'51% j'(':"*/% /-% /4'% !-(J3+'*#5% "*+% S#*I1/'*% PO-/$"*16'$"1'1C%
Chem. Rev.=%@?h=%@@ekM@>??C%
Biomimetic Applications of Metal Systems Supported by Scorpionates

413
g*'5"$Q=% uCaC%;% 8'(/4"5=%jCiC% 7@dehEC%&$)*H)N('1%-6%1/$#H/#$'=%3-*+)*I=%"*+%$'"H/):)/J%6-$%
5'/"(%*)/$-1J(%H-5N('O'1C%Coord. Chem. Rev.=%@f=%ffdMh?DC%
g*'5"$Q=% uCaC% ;% [-#*I=% ,CnC% 7@ddhEC% B)-)*-$I"*)H% H4'5)1/$J% -6% N/'$)*MH-*/")*)*I%
5-(J3+'*#5%"*+%/#*I1/'*%'*KJ5'1C%Adv. Inorg. Chem.=%h?=%@MRRC%
g/)'**'=%!C%7@ddDEC%aJ+$)+-/$)17NJ$"K-(J(E3-$"/-%H-5N('O'1%-6%/4'%n$-#N%k%5'/"(1b%)*-$I"*)H%
"*+%-$I"*-5'/"(()H%H4'5)1/$JC%Coord. Chem. Rev.=%@kD=%>?@M>fDC%
8)I#'$-"=%uC.C=%!'(*)HQ=%uCnC%;%&"$Q)*=%nC%7>??DEC%j'"H/):)/J%-6%/4'%!'/"(ńBZ
f
%i"/):'%ǔMB-*+b%
@=>MF++)/)-*%j'"H/)-*1%-6%/4'%8'ńBZ
f
%!-)'/J%-6%/4'%8'$$"3-$"/$"*'%,-5N('O%XNj
h
M
B75)5
B#/
E
f
_8'7,PE

>
C%Inorg. Chem.=%hk=%e?kDMe?kRC%
8)1H4'$=% BC% ;% B#$I5"J'$=% .CuCcC% 7>??>EC% !-+'(1% 6-$% /4'% NJ$"*-N/'$)*MH-*/")*)*I%
5-(J3+'*#5%"*+%/#*I1/'*%H-6"H/-$1C%Met. Ions Biol. Syst.=%fd=%>DkMf@DC%
8)1H4'$=%cClC=%S}$Q-I(#=%nC%;%B#$K("66=%cC%7>??dEC%.H-$N)-*"/'%H-5N('O'1%1#)/"3('%6-$%'*KJ5'%
)*4)3)/-$%1/#+)'1C%Current Bioactive Compounds=%k=%>eeM>dkC%
8-5)/H4':=%iClC=%!H^"#H4("*=%,C,C%;%a-(5=%jCaC%7>??>EC%a'/'$-5'/"(%,#3"*'MSJN'%!8'
f
.
h
%
,(#1/'$1%7!%`%!-=%lE%S$)I-*"((J%.J55'/$)K'+%2)/4%aJ+$-/$)17NJ$"K-(J(E3-$"/'7@ME%
"*+% S$)17NJ$"K-(J(E5'/4"*'1#(6-*"/'7@ME% ,"NN)*I% ^)I"*+1C% Inorg. Chem.=% h@=% dkRM
dDDC%
8-*/'H)(("M,"5N1=%uC,C%;%j"I1+"('=%.C<C%7@dddEC%c)HQ'(M)$-*M1#(6#$%"H/):'%1)/'1b%4J+$-I'*"1'%
"*+%,P%+'4J+$-I'*"1'C%Adv. Inorg. Chem.=%he=%>RfMfffC%
8-1/'$=%,C^C=%^)#=%ZC=%p)(*'$=%,CFC=%S4-$*/-*M&'//=%!C%;%a"(H$-2=%!CFC%7>???EC%,-5N('O'1%-6%
>M4J+$-OJMkM5'/4J(M@=hM3'*K-L#)*-*'%"1% 5-+'(1%6-$% /4'%mS&sM-*m%6-$5% -6%H-NN'$%
"5)*'%-O)+"1'1C%Dalton=%hkDfMhkDRC%
8$"91/-%+"%.)(:"=%uCuCjC%;%<)(()"51=%jCuC&C%7>??@EC%The Biological Chemistry of the Elements - The
Inorganic Chemistry of Life=%PO6-$+%v*):'$1)/J%&$'11=%c'2%[-$QC%
8#G)1"2"=% pC=% S"*"Q"=% !C=% !-$-M-Q"=% [C% ;% p)/"G)5"=% cC% 7@ddhEC% F% !-*-5'$)H% .)+'MP*%
.#N'$-O-H-NN'$700E% ,-5N('Ob% ,#7P
>
E7aB7fM/B#MkM)&$NKE
f
EC% J. Am. Chem. Soc.=% @@D=%
@>?edM@>?R?C%
8#G)1"2"=%pC=%S"/'+"=%FC=%!)J"14)/"=%[C=%PQ"5-/-=%pCM)C=%&"#("/=%8C=%&$"*''/4=%lCpCpC=%!'$Q('=%
FC% ;% ^'4*'$/=% cC% 7>??REC% ./$#H/#$"(% "*+% 1N'H/$-1H-N)H% H4"$"H/'$)K"/)-*% -6%

5-*-*#H('"$%H-NN'$70E%*)/$-1J(%H-5N('O'1b%'*+M-*%:'$1#1%1)+'M-*%H $+)*"/)-*%-6%
cP%/-%H-NN'$70EC%J. Am. Chem. Soc.=%@f?=%@>?kM@>@fC%
n"$H)*=% gC=% l'$*'+'=% ZC=% a"/H4)Q)"*=% gC,C=% l-(3'+"=% FC=%8$'J=% !C% ;%8-*/'H)(("M,"5N1=% uC,C%
7@dddEC%S4'%H$J1/"(%1/$#H/#$'%-6%"%$'+#H'+%Xc)8'.'_%4J+$-I'*"1'%N$-:)+'1%"*%)5"I'%
-6%/4'%"H/):"/'+%H"/"(J/)H%H'*/'$C%Structure=%e=%kkeMkDDC%
n"$*'$=% !C=% ^'2)*1Q)=% pC=% &"//'QMu"*HKJQ=% FC=% j'I()*1Q)=% uC=% .)'Q(#HQ"=% BC=% .N)H'$=% !CiC% ;%
.K"('*)'H=% !C% 7>??fEC% ./$#H/#$"(% "*+% 1N'H/$-1H-N)H% H4"$"H/'$)1"/)-*% -6% 3)1M()I"*+%
H-5N('O'1% -6% )$-*700E=% *)HQ'(700E% "*+% *)HQ'(7000E% 2)/4% /4'%
4J+$-/$)175'/4)5"K-(J(E3-$"/'%"*)-*C%Dalton Trans.=%@@R@M@@RkC%
n"$*'$=% !C=% j'I()*1Q)=% uC=% ,"11)+J=% 0C=% .N)H'$=% !CiC% ;% p'**'+J=% FCjC% 7@ddDEC%
aJ+$-/$)175'/4)5"K-(J(E3-$"/'=% "% 1-6/% "*"(-I% -6% 4J+$-/$)17NJ$"K-(J(E3-$"/'C%
&$'N"$"/)-*%"*+% H$J1/"(%1/$#H/#$'%-6% "%*-:'(% K)*H%H-5N('OC%Chem. Commun.=% @dekM
@deDC%
n'**"$)=%!C%;%!"$H4)w=%^C%7>??dEC%,#M,-5N('O'1%2)/4%.H-$N)-*"/'%^)I"*+1%"1%!-+'(1%6-$%
/4'%B)*+)*I%.)/'1%-6%,-NN'$%&$-/')*1C%Current Bioactive Compounds=%k=%>hhM>DfC%
n4-14=% &C=% im,$#K=% PCuC=%i#!'K=% iCiC=% &')/'$1'*=% uC%;% vHQ#*=% 8C!C%7@dddEC% ./$#H/#$"(% "*+%
6#*H/)-*"(% H4"$"H/'$)K"/)-*% -6% 1':'*% 1N'$5)H)+"(% :"*"+)#570lE% H-5N('O'1b%
Biomimetic Based Applications

414
N-/'*/)"/)-*% -6% "H/):)/J% 3J% 5'/4J(% 1#31/)/#/)-*% -*% /4'% HJH(-N'*/"+)'*J(% $)*I1C% J.
Inorg. Biochem.=%ek=%@fkM@hfC%
n4-14=%&C%;%&"$Q)*=%nC%7@ddREC%!)5)HQ)*I%/4'%3)*+)*I%-6%I(#/"5"/'%/-%K)*H%)*%/4'$5-(J1)*%
"*+%H"$3-OJN'N/)+"1'b%/4'%1J*/4'1)1%-6%XK
f
M7a,P
>
EBN
B#/=&$)
_\*,(%3J%)*1'$/)-*%-6%,P

>
%
)*/-% "%BMa% 3-*+%-6% /4'%3)17NJ$"K-(J(E4J+$-3-$"/-% K)*H%H-5N('O% XBN
B#/=&$)
_\*,(C% J.
Chem. Soc., Dalton Trans.=%>>R@M>>RhC%
n-++'*=%uC<C=%S#$('J=%.C=%S'(('$=%iC,C=%F+5"*=%gCSC=%^)#=%!C[C=%&"J*'=%<CuC%;%^'n"((=%uC%7@dd@EC%
S4'% >Cf% "*I1/$-5% OM$"J% 1/$#H/#$'% -6% *)/$)/'% $'+#H/"1'% 6$-5% FH4$-5-3"H/'$%
HJH(-H("1/'1C%Science=%>kf=%hfRMhh>C%
n-$$'((=% 0CBC=% ^ *'J=% FC=% &"$Q)*=% nC% ;% j4')*I-(+=% FC^C% 7@dd?EC% XB)17fM/'$/M
3#/J(NJ$"K-(J(E4J+$-3-$"/-_K)*H% "(QJ(% +'$):"/):'1b% H-5N'/)/):'% $'"H/):)/J% -6% K)*HM
H"$3-*%"*+%3-$-*M4J+$-I'*%3-*+1C%J. Am. Chem. Soc.=%@@>=%h?DRMh?DdC%
n#K)'H=%^CuC%;%n#K)'H=%8C.C=%u$C%7@ddhEC%F%i)$'H/'+%!'/"("/)-*%j-#/'%/-%/4'%.'('*)#5%F*"(-I%-6%
!'/4)5"K-('C%J. Org. Chem.=%kd=%hDd@MhDd>C%
a"(H$-2=% !CFC=%^)*+J% ,4)"=%^C!C=% i":)'1=% uCgC=%^)#=% ZC=% ['((-2(''1=%^CuC=% !H0**'1=%gCuC^C% ;%
!"331=% 8CgC% 7@ddREC% .N'H/$-1H-N)H% H4"$"H/'$)K"/)-*% -6% "% H-NN'$700E% H-5N('O% -6% "%
/4)-'/4'$M1#31/)/#/'+%N4'*-OJ(%$"+)H"(b% "%*'2% 5-+'(%6-$% I"("H/-1'%-O)+"1'C% Chem.
Commun.=%>hDkM>hDDC%
a"(H$-2=% !CFC=% ^)*+J,4)"=% ^C!C=% ^)#=% ZC=% !H0**'1=% gCuC^C=% ['((-2(''1=% ^CuC=% !"331=% 8CgC=%
.H-2'*=% 0CuC=% !H&"$/()*=% !C% ;% i":)'1=% uCgC% 7@dddEC% .J*/4'1'1=% 1/$#H/#$'1% "*+%
'('H/$-H4'5)1/$J% -6% H-NN'$700E% 1"()HJ("(+'4J+'r/$)17fMN4'*J(NJ$"K-(J(E3-$"/'%
H-5N('O'1%"1%5-+'(1%6-$%/4'% $"+)H"(%H-NN'$%-O)+"1'1C%J. Chem. Soc., Dalton Trans.=%
@ekfM@eD>C%
a"(6'*=%uCFC%;%S-(5"*=%<CBC%7@ddhEC%.J*/4'/)H%!-+'(%-6%/4'%.#31/$"/'%F++#H/%/-%/4'%j'+#H'+%
FH/):'%.)/'%-6%,-NN'$%c)/$)/'%j'+#H/"1'C%J. Am. Chem. Soc.=%@@D=%khekMkheDC%
a"55'1=%BC.C%;%,"$$"*-=%,CuC%7@dddEC%.J*/4'1)1%"*+%,4"$"H/'$)K"/)-*%-6%&1'#+-/'/$"4'+$"(%
c
>
P%"*+% c
>

.%\)*H700E% ,-5N('O'1%-6% S2-%a'/'$-1H-$N)-*"/'% ^)I"*+1b%!-+'(1%6-$%
/4'%B)*+)*I%.)/'1%-6%.':'$"(%\)*H%!'/"((-N$-/')*1C%Inorg. Chem.=%fR=%hkdfMhD??C%
a"55'1=%BC.C=%^#-=%ZC=%,"$$"*-=%!C<C%;%,"$$"*-=%,CuC%7>??>EC%\)*H%H-5N('O'1%-6%4J+$-I'*%
3-*+%"HH'N/)*I%'1/'$%1#31/)/#/'+%/$)1NJ$"K-(J(3-$"/'1C%Inorg. Chim. Acta=%fh@=%ffMfRC%
a"$/=%&CuC=%c'$1)11)"*=%FC!C=%a'$$5"**=%jCnC=%c"(3"*+J"*=%jC!C=%l"('*/)*'=%uC.C%;%g)1'*3'$I=%
iC%7@ddDEC%F%5)11)*I%()*Q%)*%H#N$'+-O)*1b%H$J1/"(%1/$#H/#$'%-6%H#H#53'$%1/'(("HJ"*)*%
"/%@CD%t%$'1-(#/)-*C%Prot. Sci.=%k=%>@ekM>@RfC%
a"$/5"**=% vC% ;% l"4$'*Q"5N=% aC% 7@ddhEC% &J$"K-(J(3-$"/'MK)*H% H-5N('O'1% 2)/4% +$#I1% "1%
()I"*+1C%Chem. Ber.=%@>e=%>fR@M>fRkC%
a"#1'$=%,C=%B)((=%gC%;%a-(5=%jCaC%7>??>EC%.)*I('M%"*+%i-#3('M,#3"*'%,(#1/'$1%)*%/4'%!#(/)N('%
PO)+"/)-*%./"/'1%Xl8'
f
.
h
_
fq=>q=@q
C%Inorg. Chem.=%h@=%@D@kM@D>hC%
a"K'1=% BC=%!"I*#1=% pCFC=% B-*":'*/#$"=%,C=% B-*":'*/#$"=%uC=% i"#/'$=% \C=%p"(Q=% pCaC%;%a-(=%
<CnC% 7@ddfEC% ,$J1/"(% 1/$#H/#$'% -6% +'-OJI'*"/'+% ^)5#(#1% N-(JN4'5#1% 1#3#*)/% 00%
4'5-HJ"*)*%"/% >C@R%t% $'1-(#/)-*b%H(#'1%6-$%"% 5'H4"*)15%6-$% "((-1/'$)H%$'I#("/)-*C%
Prot. Sci.=%>=%kdeMD@dC%
a'I'(5"**=%0C=%B'HQ=%FC=%g)H44-$*=%,C=%<')3'$/=%BC%;%B#$K("66=%cC%7>??fEC%F(QJ(K)*H%H-5N('O'1%
2)/4%"H4)$"(%"*+%H4)$"(%5-*-"*)-*)H%c=c=P%4'/'$-1H-$N)-*"/'%()I"*+1C%Eur. J. Inorg.
Chem.=%ffdMfheC%
Biomimetic Applications of Metal Systems Supported by Scorpionates

415
a'*Q'(=% nC% ;% p$'31=% BC% 7>??hEC% !'/"((-/4)-*')*1b% \)*H=% ,"+5)#5=% !'$H#$J=% "*+% ,-NN'$%
S4)-("/'1% "*+% .'('*-("/'1% !)5)HQ)*I% &$-/')*% FH/):'% .)/'% 8'"/#$'1% M% ./$#H/#$"(%
F1N'H/1%"*+%B)-(-I)H"(%05N()H"/)-*1C%Chem. Rev.=%@?h=%R?@MR>hC%

a)I#H4)=% [C=%PI"/"=% aC=%!)Q)=% pC=%["1#-Q"=% cC%;%["I)=%SC%7@dddEC%j'5-:"(%-6%/4'%3$)+I)*I%
()I"*+%"/-5%"/%/4'%c)M8'%"H/):'%1)/'%-6%Xc)8'_%4J+$-I'*"1'%#N-*%$'+#H/)-*%2)/4%a
>
=%
"1%$':'"('+%3J%ZM$"J%1/$#H/#$'%"*"(J1)1%"/%@Ch%t%$'1-(#/)-*C%Structure=%e=%khdMkkDC%
a)(('=%jC%7@ddDEC%S4'%!-*-*#H('"$%!-(J3+'*#5%g*KJ5'1C%Chem. Rev.=%dD=%>ekeM>R@DC%
a)(('=%jC%7>??>EC%!-(J3+'*#5%"*+%/#*I1/'*%)*%3)-(-IJC%Trends Biochem. Sci.=%>e=%fD?MfDeC%
a)(('=%jC=%j'/'J=%uC=%B"$/('21Q)Ma-6=%vC=%j')H4'*3'H4'$=%<C%;%.H4)*Q=%BC%7@ddREC%!'H4"*)1/)H%
"1N'H/1%-6%5-(J3+'*#5MH-*/")*)*I%'*KJ5'1C%FEMS Microbiol. Rev.=%>>=%hRdMk?@C%
a)55'(2$)I4/=% jC.C=% g)HQ5"*=% cC,C=% ^#B)'*=% ,CiC% ;% (-5-*=% gC0C% 7@dR?EC% ,4'5)H"(% "*+%
1N'H/$-1H-N)H% H-5N"$)1-*% -6% /4'% 3)*#H('"$% H-NN'$% "H/):'% 1)/'% -6% 5-((#1H% "*+%
"$/4$-N-+%4'5-HJ"*)*1C%J. Am. Chem. Soc.=%@?>=%kfeRMkfRRC%
a(":)*Q"=% !C^C=% !)J"G)=% SC=% ./"N('1=% jCuC% ;% a-(5=% jCaC% 7>??eEC% aJ+$-O)+'M&$-5-/'+% ,-$'%
,-*:'$1)-*1%-6%!-(J3+'*#5M0$-*M.#(6#$%g+I'MB$)+I'+%i-#3('%,#3"*'1b%POJI'*M
^)I"/'+%S-N-(-I)H"(%&
c
%,(#1/'$1C%Inorg. Chem.=%hD=%d@d>Md>??C%
a-(("*+=% &C^C% ;% S-(5"*=% <CBC% 7@dddEC% S4$''M, $+)*"/'% ,#700E% ,-5N('O'1b% ./$#H/#$"(%
!-+'(1%-6%S$)I-*"(M&("*"$%SJN'%@%,-NN'$%&$-/')*%FH/):'% .)/'1C%J. Am. Chem. Soc.=%
@>@=%e>e?Me>e@C%
a-(("*+=% &C^C% ;% S-(5"*=% <CBC% 7>???EC% F% ./$#H/#$"(% !-+'(% -6% /4'% SJN'%@%,-NN'$% &$-/')*%
FH/):'% .)/'b% c
>
.7/4)-("/'E.7/4)-'/4'$E% ^)I"/)-*% )*% "% ,#700E% ,-5N('OC% J. Am. Chem.
Soc.=%@>>=%Dff@MDff>C%
a-(5=%jCaC%7@dReEC%!'/"(MH'*/'$'+%-OJI'*%"/-5%/$"*16'$%$'"H/)-*1C%Chem. Rev.=%Re=%@h?@M@hhdC%
a-(5=% jCaC% 7@dd?EC% S4'% 3)-(-I)H"((J% $'(':"*/% -OJI'*% "/-5% /$"*16'$% H4'5)1/$J% -6%
5-(J3+'*#5b%6$-5% 1J*/4'/)H% "*"(-I% 1J1/'51% /-%'*KJ5'1C%Coord. Chem. Rev.=% @??=%
@RfM>>@C%
a-(5=% jCaC=% p'**'N-4(=% &C% ;% (-5-*=% gC0C% 7@ddDEC% ./$#H/#$"(% "*+% 8#*H/)-*"(% F1N'H/1% -6%

!'/"(%.)/'1%)*%B)-(-IJC%Chem. Rev.=%dD=%>>fdM>f@hC%
a-(5=% jCaC%;% (-5-*=% gC0C%7>??hEC% &$'6"H'b% B)-5)5'/)H%0*-$I"*)H% ,4'5)1/$JC%Chem. Rev.=%
@?h=%fheMfhRC%
a-(5'1=% .C% ;% ,"$$"*-=% ,CuC% 7@dd@EC% !-+'(1% 6-$% /4'% 3)*+)*I% 1)/'% )*% 3$-5-N'$-O)+"1'b%
5-*-*#H('"$% :"*"+)#57lE% N4'*-("/'% H-5N('O'1% -6% /4'% 4J+$)+-/$)17f=kM
+)5'/4J(NJ$"K-(J(E3-$"/'%()I"*+C%Inorg. Chem.=%f?=%@>f@M@>fkC%
a-*I=% iC=% \4"*I=% [C% ;% a-(5=% jCaC%7>??kEC% a'/'$-5'/"(% H#3"*'M/JN'% <8'
f
.
h
%"*+%$'("/'+%
H(#1/'$1%/$)I-*"((J%1J55'/$)K'+%2)/4%4J+$-/$)17f=kM+)5'/4J(NJ$"K-(J(E3-$"/'C%Inorg.
Chim. Acta=%fkR=%>f?fM>f@@C%
a-2"$+=% uCBC% ;%j''1=% iC,C% 7@ddDEC% ./$#H/#$"(%B"1)1%-6%B)-(-I)H"(%c)/$-I'*%8)O"/)-*C%Chem.
Rev.=%dD=%>dDkM>dR>C%
a#=%\C=%<)(()"51=%jCiC=%S$"*=%iC=%.N)$-=%SCnC%;%n-$#*=%.C!C%7>???EC%j'M'*I)*''$)*I%g*KJ5'M
!-+'(% FH/):'% .)/'1b% j':'$1)3('% B)*+)*I% -6% P
>
%"/%F53)'*/%,-*+)/)-*1%3J%"%
B)-)*1N)$'+%,-NN'$%,-5N('OC%J. Am. Chem. Soc.=%@>>=%fkkDMfkkeC%
a#"*I=%uC=%n-4=%,C%;%a-(5=%jCaC%7@ddeEC%P*%/4'%gO)1/'*H'%)*% (#/)-*%-6%i-#3(J%S4)-("/'M
B$)+I'+%i-#3('%,#3"*'1%,-*/")*)*I%/4'%a'/'$-5'/"(%X!8'
f
.
h
_%,-$'%7!%`%!-=%<EC%
Inorg. Chem.=%fD=%fkDMfD@C%

×