Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes

Article abstract of DOI:10.1039/c9dt04532e

A series of arene ruthenium iminophosphonamide complexes, [(Arene)RuCl{R₂P(NR′)₂}] (1), bearing various arenes and R,R′ substituents on the NPN ligand have been investigated as precatalysts in acetophenone transfer hydrogenation in b

Full text of DOI:10.1039/c9dt04532e

View Article Online
View Journal
Dalton
Transactions
An international journal of inorganic chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: A. M. Kalsin, T. A.
Peganova, I. S. Sinopalnikova, I. V. Fedyanin, N. Belkova, E. Deydier and R. Poli, Dalton Trans., 2020, DOI:
10.1039/C9DT04532E.
Volume 46
Number 10
14 March 2017
Pages 3073-3412
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
An international journal of inorganic chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
rsc.li/dalton
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
ISSN 0306-0012
COMMUNICATION
Douglas W. Stephen et al.
shall the Royal Society of Chemistry be held responsible for any errors
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH+, X = S, Se, Te)
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
rsc.li/dalton

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 1 of 11
View Article Online
DOI: 10.1039/C9DT04532E
A !"#$%
G(58)-4*.45 +46(2*4.: 4- )5(.,>8(-,-( .2)-*H(2 8:+2,3(-).4,-
5).)':I(+ J: 20.8(-401 414-,>8,*>8,-)14+( 5,1>'(<(*
A'(<)-+(2 GC K)'*4-=L) !).:)-) AC &(3)-,6)=) ")-) MC M4-,>)'-4N,6)=)=J "6)- OC P(+:)-4-=) Q).)'4) OC
R('N,6)=) %245 ?(:+4(2=J 4-)'+, &,'4J=5L
(5(46(+ 77.8 9)-0)2: ;7<<=
A55(>.(+ 77.8 9)-0)2: ;7<<
?@"A B7CB7DEF<7<<77777<
A *(24(* ,H )2(-( 20.8(-401 414-,>8,*>8,-)14+( 5,1>'(<(*= STA2(-(U 0#'V ;&TQ WU;XY T U= J()24-3 6)24,0* )2(-(* )-+ = W
*0J*.4.0(-.* ,- .8( Q&Q '43)-+ 8)6( J((- 4-6(*.43).(+ )* >2(5).)':*.* 4- )5(.,>8(-,-( .2)-*H(2 8:+2,3(-).4,- 4- J)*45 )-+
J)*(ZH2(( 4*,>2,>)-,'C !8( 2(*0'.* 5'()2': +(1,-*.2).( .8( >2(*(-5( ,H .[, +4*.4-5. 2()5.4,- 1(58)-4*1*= [8458 )2(
5,-.2,''(+ J: .8( J)*454.: ,H .8( QZ).,1*C #,1>'(<(* 4- [8458 J,.8 W *0J*.4.0(-.* )2( )2:' 32,0>* )2( ,-': )5.46( ,-5( .8(
-(0.2)' 8:+24+( 5,1>'(< STA2(-(U 0\V ;&TQ WU;XY T!U 4* 3(-(2).(+ 4- J)*45 4*,>2,>)-,'= .8( ')..(2 J(4-3 )J'( ., 2(+05( )
N(.,-( 64) ) *.(>[4*( 8:+24+( )-+ >2,.,- .2)-*H(2C @- .8( ,.8(2 8)-+= 5,1>'(<(* 4- [8458 ). '()*. ,-( W 32,0> 4* G( 2()+4':
5).)':I( .8( 2()5.4,- 4- .8( )J*(-5( ,H J)*(C "- .8( ')..(2 5)*(= .8( 2(*0'.* ,H N4-(.45 *.0+4(* )-+ ?P! 5)'50').4,-* *0>>,2. )-
,0.(2Z*>8(2( 5,-5(2.(+ )*:-582,-,0* 8:+2,3(- ).,1* .2)-*H(2 )**4*.(+ J: .8( J)*45 QZ).,1 ,H .8( Q&Q '43)-+= [8458
>2,1,.(* 5).)':*4* 64) >2(5,,2+4-).4,- ,H )- )'5,8,' 1,'(50'( J: 8:+2,3(- J,-+4-3C
H0-5.4,- 4* ) 52054)' >2(2(c04*4.( 2(-+(24-3 .8( 5).)':*. 8438':
(HH454(-.C
"#$%&'()$*&#
(5(-.': [( 8)6( +(1,-*.2).(+ H,2 .8( H42*. .41( .8).
]4.8 .8( +4*5,6(2: ,H 1(.)'^'43)-+ J4H0-5.4,-)' 5).)':*.*=B
.2)-*H(2 8:+2,3(-).4,- ,H N(.,-(* 8)* J(5,1( ) 8438': (HH454(-.
1(.8,+ H,2 .8( *:-.8(*4* ,H *(5,-+)2: T5842)'U )'5,8,'*C;= D "- .84*
2(3)2+= .8( Q,:,24Z"N)24:) 5).)':*.* STA2(-(U 0#'T!*+>(-UY_ )-+
*.205.02)'': *414')2 5,1>'(<(*`ZBB 8)6( +2)[- 1058 )..(-.4,-
)-+ .8( (HH(5. ,H *.205.02)' 58)-3(* ,- .8( )5.464.: )-+ ,- .8(
5).)':.45 1(58)-4*1 8)6( J((- (<.(-*46(': *.0+4(+ J,.8
(<>(241(-.)'': )-+ .8(,2(.45)'':CB;Z;7 !8( a)55(>.(+b
1(58)-4*1 H,2 J4H0-5.4,-)' 5).)':.45 8:+2,3(-).4,- J: .8(
Q,:,24Z"N)24:) 5).)':*.* 8)* J((- >,*.0').(+ ., >2,5((+ )* )
5,-5(2.(+ ,0.(2Z*>8(2( >2,.,-F8:+24+( .2)-*H(2 H2,1 .8( 1(.)'
5(-.2( ., .8( *0J*.2).( 5)2J,-:'45 5)2J,- 64) ) 8438':Z,2+(2(+
>(245:5'45 .2)-*4.4,- *.).( 4-6,'64-3 .8( '43)-+ Q\ 32,0>=B; .8(
H,21).4,- ,H [8458 4* 2(*>,-*4J'( H,2 8438 )5.464.4(* )-+ 58(1,Z
F(-)-.4,*('(5.464.4(*C \,[(6(2= .8( +(32(( ,H *:-582,-4*1 ,H
.8( 8:+24+( )-+ >2,.,- .2)-*H(2 8)* J((- H02.8(2 +4*50**(+ .,
*033(*. )'.(2-).46(': .8( (<4*.(-5( ,H ) *>(5.201 ,H >,**4J'(
2()5.4,- >).8[):* 2)-34-3 H2,1 5,-5(2.(+ ., *.(>[4*(
>2,.,-F8:+24+( .2)-*H(2= [4.8 .8( >2,.,- (4.8(2 .2)-*4.4-3
.82,038 ) '43)-+ ,2 J(4-3 +42(5.': .2)-*H(22(+ H2,1 \; ., .8(
)'N,<4+( >2,+05.C;BZ;_ "- 1,*. 5)*(* .8( >2(*(-5( ,H )- Q\
20.8(-401 414-,>8,*>8,-)14+( ST Z#:1(-(U 0#'T&8;&TQZ Z
!,'U;UY T +U 5)- 5).)':*( .2)-*H(2 8:+2,3(-).4,- ,H
)5(.,>8(-,-( 4- 4*,>2,>)-,' 0-+(2 J)*45 5,-+4.4,-*C;` "-
5,-.2)*. ., 4*,('(5.2,-45 Q,:,24Z"N)24:) 5).)':*.*= .8( Q&Q
'43)-+ 4- + 4* -,. +(>2,.,-).)J'( )-+ .8(2(H,2( -, '43)-+
)**4*.)-5( 4- .8( 8:+2,3(- .2)-*H(2 *.(> 4* >,**4J'(C ]( 8)6(
>2,>,*(+ ) 5).)':.45 5:5'( .8). 4-6,'6(* )- ,0.(2Z*>8(2( .2)-*H(2
,H .8( 8:+24+45 ).,1 H2,1 .8( !" #!$% 3(-(2).(+ 8:+24+( 5,1>'(<
ST Z#:1(-(U 0\T&8;&TQZ Z!,'U;UY T!+U ., .8( 5)2J,-:' ).,1 64)
.8( I[4..(24,-45 4-.(21(+4).( ST Z#:1(-(U 0dTQ&QUT\e#T@Z
UG(&8Y= [84'( .8( >2,.,- 4* +('46(2(+ J: .8( )'5,8,' *,'6(-.C
!84* 1(58)-4*.45 >2,>,*4.4,- [)* *0>>,2.(+ J: 1,+('
(<>(241(-.*= N4-(.45 *.0+4(* )-+ ?P! 5)'50').4,-*C A2(-(
20.8(-401 414-,>8,*>8,-)14+(* )2( ('(5.2,-Z2458 5,1>'(<(*
+0( ., I[4..(24,-45 -).02( ,H .8( ;&dTQ WZU; TQ&QU '43)-+= [8458
1)N(* .8( Bfg STA2(-(U 0TQ&QUhY 5,1>'(<(* 5,,2+4-).46(':
')J4'( )-+ *.)J4'4I(* .8(42 Big STA2(-(U 0TQ&QUYdhZ
5,0-.(2>)2.*C;i !8( Bfg 5,1>'(<(* [4.8 ('(5.2,-Z+,-).4-3 QZ
)-+ &Z*0J*.4.0(-.* )2( >2,-( ., +4**,54).4,- )-+ )2( *0*5(>.4J'(
., ('(5.2,>84'45 )..)5N ,H .8( J)*45 QZ).,1*C !8(2(H,2(= *058
('(5.2,-Z+,-).4-3 QZ )-+ &Z*0J*.4.0(-.* 1): *43-4H45)-.':
58)-3( .8( >2,>(-*4.: ,H .8( QZ).,1* ., >2,.,-).4,-= [8458
5)- 0'.41).(': 2()'4I( .8( 5,-5(2.(+ >2,.,-F8:+24+( .2)-*H(2 4-
5).)':.45 2(+05.4,- ,H N(.,-(*C
&'A'(' ()#*)+&",- ."#$!$%$) ,/ 012&",)3)*)"$ 4,* ,%"5#6 7%##!&" A8&5)*+ ,/
98!)"8)#6 :; <&-!3,- #$1'6 ==>>>= ?,#8,@6 7%##!&'
"- .84* >)>(2 [( 2(>,2. ,- .8( )5(.,>8(-,-( .2)-*H(2
8:+2,3(-).4,- [4.8 4*,>2,>)-,' 5).)':I(+ J: )2(-( 20.8(-401
414-,>8,*>8,-)14+( 5,1>'(<(* STA2(-(U 0#'T,-,UY T ./0=
#8)2. BU J()24-3 6)24,0* QZ )-+ &Z*0J*.4.0(-.* ,- .8( Q&Q
'43)-+ TAj1U= 4-5'0+4-3 N4-(.45 *.0+4(* )-+ ?P! 5)'50').4,-* 4-
*0>>,2. ,H .8( 5).)':.45 1(58)-4*1C !8( (<>',2).4,- ,H ) [4+(2
A'4(796 B&A,1&$,!1) 5) 4C!*!) 5) 4,,15!"&$!,"6 D"!-)1#!$E 5) F,%3,%#)6 DG96 .(GF6
:HI 7,%$) 5) (&1A,"")6 J=HKK F,%3,%#) 4)5)L M6 N1&"8)' O*&!3P 1!"&35,' ,3!Q388R
$,%3,%#)'/1'
8' ."#$!$%$ D"!-)1#!$&!1) 5) N1&"8)6 =6 1%) S)#8&1$)#6 KI:J= G&1!# 4)5)L HI6 N1&"8)'
%'(5.2,-45 M0>>'(1(-.)2: "-H,21).4,- T%M"U )6)4')J'(A S+(.)4'* ,H )-: *0>>'(1(-.)2:
4-H,21).4,- )6)4')J'( *8,0'+ J( 4-5'0+(+ 8(2(YC M(( ?@"A B7CB7DEF<7<<77777<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 2 of 11
View Article Online
DOI: 10.1039/C9DT04532E
A23"451
6&(%#.7 ,.80
1$%&
1$%&
123-4255,6
'(
"
1$%&
#.
#.
,6
,6
#.
#.
#.
#.
#.
#.
"
"
"
#
"
#
#
#
#
"-
"-
"-
"-
'(
"-
'(
1$%&
1$%&
123-4255,6
A
7
2
+
,
!
2&
!
"
!
"
8
8
'(
"
#
"
"
#
2&
2&
"
#.
#.
#
8
8
$%&
#.
#.
):
);
)<
)*
)(
8 2 : "#8 29 : ;=>!
8 2 : +,8 29 : ;=>!
8 2 : "#8 29 : '7
8 29 : ; 6&< *4+,
)9
8 29 : ;=>!
4@.%$ H !8( '4*. ,H Q&Q '43)-+* )-+ 0Q&Q 5,1>'(<(* (1>',:(+ 4- .84* *.0+:
2)-3( ,H 5,1>'(<(* +4HH(24-3 J: .8( -).02( ,H .8( )2(-(= Q )-+
& *0J*.4.0(-.*= 8)* 2(6()'(+ .8( >2(*(-5( ,H .[, )'.(2-).46(
1(58)-4*1*= [4.8 .8( >2(H(22(+ >).8[): 5,-.2,''(+ J: .8( Q&Q
'43)-+ J)*454.:C
I*J(%0 H @ !%& +4)32)1 ,H 'C %''4>*,4+* )2( *8,[- ). .8( `7p >2,J)J4'4.: '(6('q
8:+2,3(- ).,1* )2( ,14..(+ H,2 5')24.:C M('(5.(+ J,-+ '(-3.8* ToU )-+ )-3'(* TrUA
0sssA2(-(T5(-.2,4+U BCimD= 0j#' ;C_;miT`U= 0jQB ;CBDmDTB_U= 0jQ;
;CBmDiTB_U= QBj 0jQ; ifC;iT`U= 0jQBj&jQ; BmEC_fTEU= tTQBU D`EC7= tTQ;U D`fCEC
20:(7$: .#' ;*:)(::*&#
!8( *:-.8(*4* )-+ >2,>(2.4(* ,H .8( 5,1>'(<(* ./) )-+ + 8)6(
J((- >2(64,0*': 2(>,2.(+=;i= ;m [84'( .8( -([ 5,1>'(<(* ' )-+
0 J()24-3 .8( -,-*:11(.245)' QZ1(.8:'ZQWZ Z.,':'Z*0J*.4.0.(+
'43)-+ ; )-+ .8( '43)-+ 1 [4.8 ('(5.2,-Z[4.8+2)[4-3 QZA2L TA2L
n Z#i\_#@;%.U 32,0>*= 2(*>(5.46(':= )2( +(*524J(+ 8(2( H,2 .8(
H42*. .41(C
<.= >?#$@0:*: &+ A<4BC0B=2(D-@!-<,/ /3&7=<,C0=E47F < '= .#' A< /
4?80#0=2(D-@!-<,/A%G=!E47F < 0=H
!8( 0-N-,[- 414-,>8,*>8,-)14-( 1 [)* c0)-.4.).46(':
,J.)4-(+ H2,1 .8( 5,22(*>,-+4-3 +4)14-,>8,*>8,-401 *)'.
S&8;&TQ\A2LU;YR2;f J: +(>2,.,-).4,- [4.8 +4(.8:')14-(C ". [)*
H0'': 58)2)5.(24I(+ J: QG *>(5.2,*5,>: )-+ ('(1(-.)'
)-)':*4*C
!8( -([ )2(-( 20.8(-401 5,1>'(<(* ' )-+ 0 [(2(
*:-.8(*4I(+ )55,2+4-3 ., .8( >2(64,0*': >0J'4*8(+ >2,5(+02(=;m
4C(C J: 2()5.4-3 STA2(-(U 0#';Y; [4.8 .8( N-,[- 414-,>8,*>8,Z
-)14-( ;;E ,2 .8( -([ >2,'43)-+ 1= 2(*>(5.46(':= +(>2,.,-).(+
[4.8 B (c046C Q)\G?M 4- J(-I(-( TM58(1( BUC
I*J(%0 !C @ !%& +4)32)1 ,H 0C %''4>*,4+* )2( *8,[- ). `7p >2,J)J4'4.:= 8:+2,3(-
).,1* )2( ,14..(+ H,2 5')24.:C @-': ,-( H2)31(-. ,H .8( +4*,2+(2(+ 5:1(-( )-+
@%. H2)31(-.* 4* *8,[-C M('(5.(+ J,-+ '(-3.8* ToU )-+ )-3'(* TrUA
0sssA2(-(T5(-.2,4+U BCi_m= BCimDq 0j#' ;C_BBT;U= 0jQB ;CB_mTfU= 0jQ;
;CB_`T`U= QBj 0jQ; imCET;U= 0jQBj&jQ; BmBCfT`U= tTQBU D`mCm= tTQ;U D`EC`C
!8( 4*,').(+ >2,+05.* [(2( H0'': 58)2)5.(24I(+ J:
10'.4-05'()2 QG *>(5.2,*5,>: )-+ ('(1(-.)' )-)':*4*= )-+
.8(42 1,'(50')2 *.205.02(* [(2( 5,-H421(+ J: *4-3'( 52:*.)' hZ
2): +4HH2)5.4,- *.0+4(* TP4302(* B )-+ ;= !)J'( MB 4- %M"UC
#,1>'(<(* ' )-+ 0 (<84J4. ) .82((Z'(33(+ >4)-, *.,,'
3(,1(.2: [4.8 ) >*(0+, ,5.)8(+2)' 5,-H4302).4,- ,H .8( '43)-+*
)2,0-+ .8( 20.8(-401 ).,1C !8(42 *.205.02)' >)2)1(.(2* )2(
*414')2 ., .8,*( ,H #iG(i )-+ Z5:1(-( )-)',30(* ./) )-+ +=
2(*>(5.46(':= H,2 [8458 ) +(.)4'(+ *.205.02)' )-)':*4* 8)*
>2(64,0*': J((- 2(>,2.(+C;i= ;m %<>(5.(+':= .8( 0jQ )-+ 0j#'
+4*.)-5(* )2( *'438.': *8,2.(2 H,2 5,1>'(< 0 T;CB_iTfU o )-+
;C_BBT;U o= 2(*>(5.46(':U .8)- H,2 ' T;CB```TB_U o )-+
;C_;miT`U o= 2(*>(5.46(':U= J(5)0*( ,H .8( (HH(5. ,H .8( Z
5:1(-( '43)-+ )-+ .8( ('(5.2,-Z[4.8+2)[4-3 QZ)2:' 32,0>* ,H
"
#.
#.
$%&'()
$%&
!
"
#
"
!
-. 6'76123 !454
"#
-"
+
'(
#
'(
)*
"#
"
**+,
$%&'()
#.
#.
A/0
!
"
#
"
!
-. /0123 !454
"#
-"
,
**+,
#
A/0
)(
.8( 414-,>8,*>8,-)14+( 1,4(.:C A*
) 2(*0'. ,H .8(
"#
+(',5)'4I).4,- ,H .8( 0->)42(+ ('(5.2,- +(-*4.: ,H .8( -4.2,3(-
).,1* ,- .8( QZ)2:' *0J*.4.0(-.*= .8( >:2)14+)'4*).4,- ,H .8(
>)@080 H M:-.8(*4* ,H 5,1>'(<(* ' )-+ 0C
! k T' (&*)C= ;7B;= 99= BZD
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 3 of 11
View Article Online
DOI: 10.1039/C9DT04532E
6&(%#.7 ,.80
A23"451
2B
2B
2B
$%&'()
!"?*&
;& 7!@0A
!
"
!
"
!
"
8
8
8
"
#
"
#
"
#
2&
-
5!#/
8
8
8
;'74 *
):1(
=:1(
>:1(
>)@080 !H u(-(2)' *58(1( H,2 3(-(2).4,- ,H 8:+24+( 5,1>'(<(* !./0C
-4.2,3(- ).,1* H,2 '=0 4* *1)''= tTQU n D`mCm j D`EC`r= *414')2':
., 5,1>'(<(* .LML+C !8( 0TBUQTBU&TBUQT;U 1(.)'')5:5'( 4*
*'438.': J(-. J: 7C`r T 'U )-+ fC;r T 0U H2,1 >')-)24.:C !8( Z
5:1(-( 24-3 )-+ ,-( ,H .8( @%. H2)31(-.* 4- 0 )2( +4*,2+(2(+
)1,-3 .[, >,*4.4,-* [4.8 )'1,*. (c0)' ,550>)-54(* H,2 ()58
5,1>,-(-. T2(H4-(+ )* 7C_EA7C`BUC
A-)',3,0*': ., M )-+ )=;i .8( &8 32,0>* ). .8( >8,*>8,20*
).,1 4- .8( 5,1>'(< ' (<>(24(-5( +(3(-(2).46( (<58)-3( +0(
., H)54'( 58',24+( +4**,54).4,- [4.8 )- (<58)-3( 2).( 5,-*.)-. U(<
n DC_ *ZB )-+ ) u4JJ* )5.46).4,- (-(23: vV(< n BiC` N5)'F1,'=
w
I*J(%0 KC DB&VB\X QG 1,-4.,24-3 ,H .8( 2()5.4,- ,H R [4.8 Q)\G?MF4&2@\ 4-
#i?iC #,-+4.4,-*A #i?i T7C` 1$U= !&2@\ TB7 x$U= . T7C7; 11,'U= Q)\?GM T; G 4-
!\P= B` }$U= .F!&2@\ n BFf= \G?MF . n BC`C
[8458 4* ;C7 N5)'F1,' 8438(2 .8)- .8). H,2 ) 8)64-3 .[,
+,-).4-3 QZG( *0J*.4.0(-.* TP4302( MB= !)J'( M;UC !8( *)1(
(<58)-3( H,2 0 4* (<>(5.(+ ., J( (6(- *',[(2 .8)- H,2 += H,2
w
z-'4N( .8( Z5:1(-( )-)',30( !+= .8( 8:+24+( !. 4* *.)J'(
H,2 +):*C ". +,(* -,. +(5,1>,*( ,2 0-+(23, 2()22)-3(1(-. 4-.,
)- 4*,1(245 5:5',8(<)+4(-:' 5,1>'(<= (6(- 0>,- >2,',-3(+
8().4-3 ). i7r# T.8,038 .2)5(* ,H .8( 414-,>8,*>8,-)14-( A
+0( ., Q&Q '43)-+ >2,.,-,':*4* [(2( 64*4J'( )H.(2 B +):U=
)>>)2(-.': +0( ., *.(245 J0'N ,H .8( #iG(i '43)-+C #,1>'(< !.
[)* 4*,').(+ H2,1 .8( 2()5.4,- 14<.02( )-+ 58)2)5.(24I(+ J: B\=
[8458 .8( vV(< 4- J(-I(-( [)* (*.41).(+ ., J( 32().(2 .8)-
BfC` N5)'F1,'C;i "-+((+= -, (<58)-3( H,2 0 [)* +(.(5.(+ 4-
#i?i= [84'( (6(- 4- .8( 2(').46(': >,')2 #?#'D .8( ,1$C,Z\ ,H .8(
.[, +4HH(2(-. >8(-:' 32,0>* )2( ,J*(26(+ *(>)2).(': TP4302(
M;U= 4-+45).4-3 ) 6(2: *',[ (<58)-3(C
<M= N0#0%.$*&# .#' :$.M*7*$? &+ A<A%0#0=2(<,-,=OF :P0)*0:H
]( 8)6( 2(5(-.': +(*524J(+ .8( 3(-(2).4,- ,H ) 8:+24+(
5,1>'(< ST Z#:1(-(U 0\TQ&QUY T!+= Q&Q n &8;&TQZ Z!,'U;U
H2,1 .8( 5,22(*>,-+4-3 58',24+( + )-+ *,+401 4*,>2,>,<4+( 64)
WZ\ ('414-).4,- 4- .8( 4*,>2,>,<4+( 4-.(21(+4).( ST Z
#:1(-(U 0T@!&2UTQ&QUY TK+UC;` \(2( [( *8,[ .8). .84*
>2,5(+02( 4* ,>(2).4,-)' H,2 .8( 3(-(2).4,- ,H ) [4+(2 )22): ,H
20.8(-401 8:+24+(* STA2(-(U 0\TQ&QUY T!./0U H2,1 .8(
5,22(*>,-+4-3 58',24+( 5,1>'(<(* ./0= )'.8,038 .8( *.)J4'4.:
,H .8( >2,+05.* 4* 6(2: +4HH(2(-.C
B
DB& )-+ BD# QG *>(5.2,*5,>: TP4302(* M_UC "- .8( \ QG
*>(5.201= .8( 0\ *43-)' 4* ,J*(26(+ ). { ZDC;` 4- >02( J(-I(-(Z
+iC ?(*>4.( 1)-: )..(1>.*= [( [(2( -,. )J'( ., ,J.)4- *04.)J'(
52:*.)'* H,2 )- hZ2): )-)':*4*C
(>')54-3 .8( >8(-:' &Z*0J*.4.0(-.* [4.8 1,2( ('(5.2,-Z
+,-).4-3 (.8:' 32,0>* 4- M +,(* -,. )HH(5. .8( 8:+24+( !M
3(-(2).4,- .41( H2,1 .8( 5,22(*>,-+4-3 4*,>2,>,<4+( KM= [84'(
4. 5)0*(* *4+( 2()5.4,-* ., ,5502 TP4302( M`UC !8( 4-4.4)'':
,J*(26(+ 2(*,-)-5( ). { i_C` 4- DB& QG TP4302( M`TJUU )-+ .8(
*(>.(. ,H #XG(; ). { _C`E 4- B| QG TP4302( MiU [(2( )**43-(+
!8( 58',24+( 5,1>'(<(* ./0 [(2( .2().(+ [4.8 BZBC` (c046C
,H Q)\G?M 4- #i?iF!&2@\ n `77FB7Z_7 x$ ). 2,,1 .(1>(2).02(
)-+ .8( 3(-(2).4,- ,H .8( 5,22(*>,-+4-3 8:+24+( 5,1>'(<(* !./
0 TM58(1( ;U [)* 1,-4.,2(+ J: DB& )-+ B\ QG *>(5.2,*5,>:C
!8( H,21).4,- ,H STyiG(iU 0\T&8;&TQZ Z!,'U;UY T!.U >2,5((+*
-!& .8( ,J*(26)J'( 4*,>2,>,<4+( 4-.(21(+4).( STyiG(iU 0T@4&2UZ
T&8;&TQZ Z!,'U;UY TK.U= [8458 >2(+,14-).(* 4- .8( 14<.02(
+024-3 .8( H42*. B` 14- ,H .8( 2()5.4,-= )-+ 4* 5,1>'(.( [4.84- ;
82* TP4302( DUC #,1>'(< K. [)* 4+(-.4H4(+ J: .8( 58)2)5.(24*.45
*(>.(. ,H .8( 1(.8:-( 32,0> ,H .8( 4*,>2,>,<: '43)-+ 4- .8(
4-4.4)' B\ QG *>(5.201 TP4302( MDUC
B
., KM= [84'( .8( DB& QG *4-3'(. ). { iDCD )-+ .8( \ QG
2(*,-)-5( ). { j_CBf TP4302(* MmU [(2( )..24J0.(+ ., !MC A>)2.
H2,1 H([ 14-,2 41>024.4(*= .84* 2()5.4,- )'*, :4('+* QM=
58)2)5.(24I(+ J: ) DB& QG 2(*,-)-5( ). { DECf )-+ J: )
+,0J'(. ,H *(>.(.* ). { _C`D TDT&\ n EC; \I= DTy\ n iC7 \IU 4- .8( B\
QG *>(5.201= [8458 )>>()2* ., 5,22(*>,-+ ., .8( QZ!&2
*0J*.4.0.(+ )14-,>8,*>84-( ,<4+( %.;&T@UZQT!&2U!,' TP4302( Mm=
4-*(2.UC !8( )1,0-. ,H QM 4-52()*(* *410'.)-(,0*': [4.8 .8(
3(-(2).4,- ,H !M= *033(*.4-3 .8). 4. H,21* J: .8( 5,1>(.4-3
$%&
"
?#/
$%&
#
!
$%&
,6
!
!
"
"
5?#/
,6
,6
5?#/
#
?#/51
1
"
1
5?#/
"
"
#
,6
5
?#/
$%&
5
$%&
$%&
,6
,6
4;
=;
>)@080 KC &2,>,*(+ 1(58)-4*1 ,H .8( H,21).4,- ,H QMC
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
T' (&*)C= ;7BD= 99= BZD k K
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 4 of 11
View Article Online
DOI: 10.1039/C9DT04532E
A23"451
6&(%#.7 ,.80
&
&
&
!"?
&
$%&'()
!"?*&
;& 7!@0A
!
"
!
"
!
"
8
8
8
!"?
8
"
#
"
#
"
#
!
2&
-
!
A
5!#/
8
"
#.
#.
#.
"
8 8
"
"
8
8
8
#
;'74 *
#
#.
#.
=(
#.
#.
#.
#.
#.
)(
29 : ; 6&< *4+,
>(
@(
@(8
>)@080 QC u(-(2).4,- ,H .8( 8:+24+( !0 )-+ 4.* 2()22)-3(1(-. ., U0WU0VC
-05'(,>84'45 )..)5N ,H .8( H2(( 4*,>2,>,<4+(Z)-4,- ,- .8( DCm;U TP4302( MB;UC AH.(2 D +):*= !' [)* )'1,*. 5,1>'(.(':
('(5.2,>84'45 >8,*>8,20* ).,1 H,'',[(+ J: .8( &ZQ J,-+ +(5,1>,*(+ ., )14-,>8,*>84-( ,<4+( &8;&T@UTQ\G(U TQ'= {
5'()6)3( )-+ 4*,>2,>:' 32,0> 1432).4,- ,-., .8( -4.2,3(- ).,1 ;`CDU )-+ 414-,>8,*>8,-)14-( ; T{ _C7U= >'0* 0-N-,[-
TM58(1( DUC @-5( .8( (<5(** ,H @!&2Z 4* 5,-*01(+= !M 4* 2).8(2 5,1>,0-+* [4.8 DB& QG *43-)'* ). { D`C` )-+ fCm= )>>)2(-.':
*.)J'( 4- *,'0.4,-C !84* *4+( 2()5.4,- 2(+05(* .8( :4('+ ,H .8( +0( ., >2,.,-).4,- ,H .8( QG( 32,0>= H,'',[(+ J: Q&Q '43)-+
8:+24+( 5,1>'(< !M= )-+ )HH(5.* .8( 5).)':.45 >(2H,21)-5( ,H M +(5,,2+4-).4,- )-+ )'5,8,':*4*C
T*(( J(',[UC z-H,2.0-).(':= (6(- +(52()*4-3 .8( )1,0-. ,H
!8( H,21).4,- ,H .8( 8:+24+( 5,1>'(< ST Z
J)*( ., BC7 (c046C +4+ -,. *0>>2(** .84* *4+( 2()5.4,- #:1(-(U 0|T&8;&TQA2LU;UY T!TU 4* *',[(2 .8)- .8). ,H .8(
5,1>'(.(':= )-+ J(*4+(* !M= .8( >2,+05. 5,-.)4-(+ ;7Zi7p ,H N-,[- Z5:1(-( 8:+24+( !+=;` +0( ., .8( >2(*(-5( ,H )55(>.,2
QM 4- +4HH(2(-. (<>(241(-.*C
*0J*.4.0(-.* 4- .8( QZA2:' 32,0>* TP4302( MBDUC !8( 4*,>2,>,<4+(
ST Z#:1(-(U 0T@4&2UT&8;&TQA2LU;UY
TKTU=
!8( 2()5.4,- ,H K) [4.8 4*,>2,>)-,' 4- .8( >2(*(-5( ,H ) 4-.(21(+4).(
*.2,-3 J)*( TP4302( MfU >2,5((+* 6(2: c045N': '()+4-3 1,*.': ., 58)2)5.(24I(+ J: ) DB& 2(*,-)-5( ). { _DC;= [)* *.4'' >2(*(-.
+(5,1>,*4.4,- >2,+05.= -)1(': .8( )14-,>8,*>84-( ,<4+( )H.(2 ; 8 ). 2,,1 .(1>(2).02( )-+ 5,0'+ J( 58)2)5.(24I(+ J: B\
&8;&T@UTQ\G(U TQ)= { ;`CDUC !8( 4*,>2,>,<4+( 5,1>'(< K) [)* QG TP4302( MB_UC #,1>'(< !0 4* 2(').46(': *.)J'( )-+ [)*
-,. +(.(5.(+ (6(- )H.(2 ,-': ` 14- )H.(2 J)*( )++4.4,-C !8( 58)2)5.(24I(+ !" #!$% J: DB& )-+ B\ QG TP4302( MB`UC \,[(6(2=
5,22(*>,-+4-3 8:+24+( 5,1>'(< STyiG(iU 0|T&8;&TQG(U;UY 4. *',[': 4*,1(24I(* ., .8( 14<.02( ,H 5:5',8(<)+4(-:'
T!SU= 58)2)5.(24I(+ J: ) DB& QG *43-)' ). { _ECf )-+ 0\ 5,1>'(<(* U0= U0V TY& `DCD= `DCm= P4302( MBDU= *414')2': ., !+
2(*,-)-5( ). { Z_CB; 4- B\ QG TP4302( Mf= 4-*(2.U= [)* ,J*(26(+ TM58(1( _UC
4- ) 2(').46( )1,0-. ',[(2 .8)- B7p [84'( .82(( )++4.4,-)'
". 4* -,.([,2.8: .8). (<5(** ,H J)*( T~ B (c046C Q)\G?MU
14-,2 41>024.4(* [4.8 DB& QG 2(*,-)-5(* ). { D;Cf= _mCi= `;Cm 2(*0'.* 4- ) 5,-5,14.)-. .2)-*(*.(24H45).4,- ,H .8( 5)2J,(.8,<:
5,0'+ -,. J( 4+(-.4H4(+C #,1>'(< !) 5)- )'.(2-).46(': J( *0J*.4.0(-.* ., H,21 1,-,Z T!0VU )-+ +4Z T!0VVU 5)2J,4*,>2,>,<:
,J.)4-(+ J: 2()5.4-3 ) [4.8 B (c046C ,H Q)R\%.D 4- J(-I(-(Z+i +(246).46(*= 0'.41).(': 3464-3 .8( 14<.02( ,H .8( 8:+24+(
TP4302( ME)U=;` >2(*(-.4-3 .8( *)1( 58)2)5.(24*.45 2(*,-)-5(* ). 5,1>'(<(* ST Z#:1(-(U 0\T&8;&TQZ Z#i\_#@@ U;UY T n %.= 4&2U
{ _ECf 4- DB& QG )-+ ). { Z_C7E 4- B\ QG TP4302( MEJUC !80* TP4302( MBiUC
.8( 8:+24+( 5,1>'(< !) 4* 4-+((+ 3(-(2).(+ 4- .8( 2()5.4,- ,H
!, *011)24I(= .8( )J,6( (<>(241(-.* +(1,-*.2).( .8). .8(
) [4.8 4*,>2,>,<4+(= 8,[(6(2 +0( ., .8( 8438': J)*45 QZ 2()5.4,- ,H ./0 [4.8 *,+401 4*,>2,>,<4+( '()+* ., .8(
).,1*;m 4. 8)* 6(2: ',[ *.)J4'4.: 4- .8( >2(*(-5( ,H 4*,>2,>)-,'= 5,22(*>,-+4-3 8:+24+( 5,1>'(<(* !./0= )>>)2(-.':= -!&
>(28)>* J(5)0*( ,H 4.* H)54'( >2,.,-).4,- )-+ H02.8(2 &ZQ J,-+ 4*,>2,>,<4+( 4-.(21(+4).(*= *414')2': ., [8). [)* ,J*(26(+
)'5,8,':*4* ., H,21 .8( )14-,>8,*>84-( ,<4+(C "-+((+= ) ()2'4(2 H,2 !+C \,[(6(2= .8( *.)J4'4.: ,H !./0 0-+(2 .8( 2()5.4,-
*',[': +(5,1>,*(* ., )14-,>8,*>84-( ,<4+( 4- 4*,>2,>)-,' 5,-+4.4,-* +4HH(2* *.2,-3': H2,1 !. T*.)J'( H,2 +):*U ., 8)2+':
(6(- 4- .8( )J*(-5( ,H ) J)*( ). 2,,1 .(1>(2).02( TP4302( MB7UC ,J*(26)J'( !)C A1,-3 .8( 8(<)1(.8:'J(-I(-( 5,1>'(<(* !./'=
#,1>'(< '= 8)64-3 ,-': ,-( J)*45 QZG( 32,0>= 2()5.* [4.8 .8,*( [4.8 1,2( J)*45 QZ).,1*= !) )-+ !'= )2( '(** *.)J'( +0(
J)*45 4*,>2,>)-,' 4- ) 1058 5'()-(2 [): TP4302( MBBU ., 346( ., H)54'( >2,.,-).4,- )-+ )'5,8,':*4* J: 4*,>2,>)-,'C A'.8,038
>2(+,14-)-.': .8( 8:+24+( 5,1>'(< !' -!& .8( 4*,>2,>,<4+( !M )>>()2(+ ., J( ,H 5,1>)2)J': 8438 *.)J4'4.: )* !.= .8(
4-.(21(+4).( K'= [8458 4* ,J*(26(+ 4- .8( H42*. 14-0.(* ). { _iCi *.(245)'': 1,2( )55(**4J'( >8,*>8,20* ).,1 4- .84* Q&Q '43)-+
4- .8( DB& QG *>(5.201C #,1>'(< !' +(5,1>,*(* 4- .8( 4* >2,-( ., @!&2Z -05'(,>84'45 )..)5N= 2(*0'.4-3 4- >)2.4)'
>2(*(-5( ,H 4*,>2,>)-,' 1,2( *',[': .8)- !)= )-+ .8(2(H,2( [)* +(32)+).4,- ,H .8( 4-.(21(+4).( KM ., .8( )14-,>8,*>84-(
B
0\
58)2)5.(24I(+ !" #!$% J: DB& QG T{ _BCDU )-+ \ QG T{
Z
,<4+( QM= .80* 2(+054-3 .8( :4('+ ,H .8( 8:+24+( 5,1>'(< !MC
5
2B
2B
2B
2B
A5?#/1
15?#/1
$%&
#.
!
"
$%&
#.
!
"
!
$%&
#.
!
"
"
"
5
"
-
-
"
$%&
"
$%&
-
#
#
5
#
#
$%&
$%&
$%&
#.
#.
#.
#.
#.
-B5C
3
=
>
>)@080 UC u(-(2).4,- ,H .8( 8:+24+(* ! 64) +4**,54).4,- ,H @!&2Z H2,1 K H,'',[(+ J: 2,.).4,- )-+ 8:+24+( .2)-*H(2C
Q k T' (&*)C= ;7B;= 99= BZD
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 5 of 11
View Article Online
DOI: 10.1039/C9DT04532E
6&(%#.7 ,.80
A23"451
)J,6(C ". 4* 41>,2.)-. ., 0-+(2'4-( .8). .8( 4-50J).4,- >(24,+ 4*
-((+(+ ., c0)-.4.).46(': .2)-*H,21 .8( >2(5).)':*. ., .8(
)5.46( *>(54(* !C Q,.)J':= [( 8)6( -, (64+(-5( ,H +)2N(-4-3 ,H
.8( *,'0.4,- [4.8 H,21).4,- ,H 1(.)''45 -)-,>)2.45'(* T4- H)5.=
.8( *,'0.4,- 5,',02 J(5,1(* H)4-.(2 )* .8( 8:+24+(* ! )2( '(**
4-.(-*(': 5,',02(+ .8)- .8( 5,22(*>,-+4-3 >2(502*,2* UC
!8( -).02( ,H .8( QZ*0J*.4.0(-.* )-+ ZiZ)2(-( )HH(5.* .8(
4-4.4)' )5(.,>8(-,-( 8:+2,3(-).4,- 2).(= [8458 4* 4-
c0)'4.).46(': )55,2+)-5( [4.8 .8( 2).( ,H ÅZ\ ('414-).4,- H2,1 K
., !A 1,2( +,-).4-3 QZ32,0>* )-+ '(** J0'N: )2(-( *43-4H45)-.':
41>2,6( .8( 5).)':*. >(2H,21)-5(C !8( ',[(2(+ )5.464.: ,H M
5,1>)2(+ ., . 4* +0( ., >)2.4)' +(5,1>,*4.4,- ,H .8(
>2(5).)':*. +024-3 3(-(2).4,- ,H .8( 8:+24+( *>(54(* !M= )*
1(-.4,-(+ 4- *(5.4,- TJUC M414')2':= .8( 2)>4+ )5.464.: +(5):
,J*(26(+ [8(- 0*4-3 ) 4* 5)0*(+ J: *.)J4'4.: 4**0(* H,2 !)C
P,2 ()58 5,1>'(<= .8( N4-(.45 +).) ). +4HH(2(-. .(1>(2).02(*
TP4302( MBmU [(2( ,J.)4-(+ ., 5)'50').( .8( )5.46).4,-
>)2)1(.(2* ,H .8( 2()5.4,- H2,1 %:24-3 >',.* TP4302( _UC !8( ',[
*.)J4'4.: ,H ) 4- J)*45 4*,>2,>)-,'= (*>(54)'': ). ('(6).(+
.(1>(2).02(*= +4+ -,. )'',[ 0* ., 20- )- %:24-3 )-)':*4* H,2 .84*
*:*.(1 )* 4. 2)>4+': +(32)+(+ )J,6( _7r# TP4302( MBm5UC P,2 !M
.8( 5).)':.45 2(*0'.* [(2( '(** 2(>().)J'(= .8(2(H,2( H,2 J04'+4-3
.8( %:24-3 >',. [( 0*(+ .8( )6(2)3( ,H .8( .[, 1,*. 5,-*4*.(-.
2).( 5,-*.)-.* ,J.)4-(+ ). ()58 .(1>(2).02(C
3.M70 H (*0'.* ,H .8( 5).)':.45 .2)-*H(2 8:+2,3(-).4,- ,H )5(.,>8(-,-( J: ./+CS)Y
-%0).$
.7?:$
.
!
*#)L
4&#Z0%:*&#L [
"
&M:L @/
8*#
B;7
i7
`
9HU @
_CE
@
fCi
HU @
B;Cf
iCB
! @
B`
K @
Q @
;;Ci
BDCD
__C`
;fC_
;_CB
i_CD
;iC`
BmCD
_`C_
D7C`
DBCm
m_CE
7C7f;
7C7_f
7CD`_
7CBDD
7CB77
7CDDi
M
)AMF
;Cm
_C_
ECf
BiCD
iC_
;mCm
BDCD
EC;
D`C`
BfC_
BBCB
DfC;
_7CB
;;CD
BiCD
_f
'
`
0
+A)F
D7
B`
`CB
B`CE
;iCf
S)Y M.)-+)2+ 5,-+4.4,-* A ;DD }$ ,H )5(.,>8(-,-( T; 11,'U )-+ ;;i }$ ,H 4-.(2-)'
*.)-+)2+ T+,+(5)-(U 4- ` 1$ ,H *,'6(-. TS&8#@G(Y n DCiisB7ZB GU= 7C7; 11,' ,H
0 5).)':*. TS 0Y n _sB7ZD GUUq B` x$ Q)\G?M T;G 4- !\PU= Q)\G?MF 0 n BC`q $4-5
j
.8( 5,-+4.4,-4-3 .41( É_7r# J(H,2( .8( *0J*.2).( )++4.4,-= U,J* j .8( >*(0+,ZH42*.
,2+(2 2).( 5,-*.)-.C SJY 7C7B 11,' ,H 0 5).)':*. TS 0Y n ;sB7ZD GUUC S5Y (*0'.* H2,1
2(HC ;`
C
@[4-3 ., .8( J0'N4(2 )2(-( '43)-+= .8( 8(<)1(.8:'J(-I(-(
5,1>'(< K. 0-+(23,(* WZ8:+24+( ('414-).4,- ). ) 5,-*4+(2)J':
*',[(2 2).( .8)- 4.* Z5:1(-( 5,0-.(2>)2. K+=;` [84'( .84* )'*,
>2(6(-.* .8( 5,22(*>,-+4-3 8:+24+( *>(54(* !. H2,1
.2)-*H,214-3 ., .8( 4*,1(245 Big Ä`Z5:5',8(<)+4(-:'
5,1>'(<(*= 0-'4N( .8( Z5:1(-( 5,1>'(<(* !0 )-+ !+C !8(
('(5.2,-Z[4.8+2)[4-3 QZ*0J*.4.0(-.* 4- K 2(.)2+ .8( ÅZ8:+24+(
('414-).4,- ., ! TK0 -# K+ )-+ K. -# K) )-+ K'U )-+ 4* 4- '4-( [4.8
,J*(26).4,-* )J,0. .8( 58',24+( (<58)-3( 2).(* 4- 5,1>'(<(*
C;i A* [( 8)6( >2,>,*(+ 2(5(-.': H,2 .8( Z5:1(-( 8:+24+(
5,1>'(< !+=;` .8( 3(-(2).4,- ,H ! 2(c042(* 4*,>2,>,<4+( '43)-+
+4**,54).4,- ., .8( 5,22(*>,-+4-3 5).4,-45 *>(54(* B )-+ AXFY=
.8( 4-.(21(+4).( )-+ .8( 2(*.4-3 *.).( 4- .84* >2,5(**=
2(*>(5.46(': TM58(1( `UC
P,2 5).)':*. += N4-(.45 (<>(241(-.* [4.8 +4HH(2(-. S 0Y 8)+
+(1,-*.2).(+ .8). .8( 2).( ')[ 4* H42*. ,2+(2 4- 5).)':*.= )* [(''
)* H42*. ,2+(2 4- N(.,-(C;` P,2 5,1>'(<(* ./0= [( 8)6(
.8(2(H,2( )**01(+ .8( *)1( 2).( ')[ )-+ -, )++4.4,-)' N4-(.45
(<>(241(-.* [4.8 6)24).4,- ,H S 0Y [(2( 5)224(+ ,0.C !8(
)5.46).4,- (-.8)'>: v[w )-+ (-.2,>: v9w +).) H,2 .8( 2).(Z
+(.(214-4-3 *.(> .80* ,J.)4-(+ )2( *011)24I(+ 4- !)J'( ;C
!8( )5.46).4,- >)2)1(.(2* ,J.)4-(+ 4- .8( >2(*(-5( ,H .8(
QZA2:' *0J*.4.0.(+ >2(5).)':*.* T .= M= 0= +U )2( [4.84- -)22,[
2)-3(* TECmjBBCm N5)'F1,' H,2 v[w )-+ DBjD` 5)'FT1,'sKU H,2
v9wUC !84* *033(*.* .8( ,55022(-5( ,H ) *414')2 5).)':.45
1(58)-4*1 H,2 .8(*( 5,1>'(<(*= [8458 )>>)2(-.': 4-6,'6(* .8(
8:+24+( *>(54(* ! )-+ .8( I[4..(24,-45 4-.(21(+4).( B )*
>2(64,0*': 4-6(*.43).(+ J: ) 5,1J4-).4,- ,H (<>(241(-.)' )-+
5,1>0.).4,-)' 1(.8,+* H,2 .8( + *:*.(1C;` !8( )5.46).4,-
(-.8)'>4(* H,2 . )-+ 0 )2( 1()-4-3H0'': 8438(2 .8)- .8). H,2
+= 4- '4-( [4.8 .8( 2(.)2+).4,- (HH(5. ,H .8( J0'N4(2 #iG(i )2(-(
'43)-+ )-+ .8( ('(5.2,-Z[4.8+2)[4-3 QZ*0J*.4.0(-.*C
<)= 3%.#:+0% @?'%&J0#.$*&# &+ .)0$&P@0#&#0 ).$.7?:0' M? ./0H
A'' .8( 5,1>'(<(* ./0 8)6( J((- .(*.(+ 4- .2)-*H(2
8:+2,3(-).4,- ,H )5(.,>8(-,-( 4- 4*,>2,>)-,' [4.8 )++4.4,- ,H
BC` (c046C Q)\G?M ). _7r# )-+ .8( 2(*0'.* [(2( 5,1>)2(+ .,
.8,*( 2(>,2.(+ H,2 +;` T!)J'( BUC !8( 5,-+4.4,-* T.(1>(2).02(=
4-50J).4,- .41( )H.(2 .8( )++4.4,- ,H J)*(U 0*(+ H,2 .8(
3(-(2).4,- ,H .8( 5).)':.45)'': )5.46( 8:+24+( 5,1>'(<(* T!./+U
[(2( 4- )55,2+)-5( [4.8 .8( 1,+(' (<>(241(-.* +(*524J(+
!8( )5.46).4,- >)2)1(.(2* H,0-+ H,2 5,1>'(< '= ,- .8(
,.8(2 8)-+= +4HH(2 *43-4H45)-.':C !8( 8438(2 v[w TBECBÇ7Cf
N5)'s1,'ZBU )-+ .8( *1)''(2 -(3).46( v9w TZmÇD 5)'s1,'ZBsKZBUU )2(
4-+45).46( ,H ) +4HH(2(-. 2).(Z+(.(214-4-3 .2)-*4.4,- *.).(= '(**
8438': ,2+(2(+ .8)- H,2 .8( A!#ZQZA2:' 5,1>'(<(*C !8(2(H,2(=
3.M70 !H !8( )5.46).4,- >)2)1(.(2* ,H )5(.,>8(-,-( 8:+2,3(-).4,- [4.8
5,1>'(<(* ./+ 4- .8( >2(*(-5( ,H J)*(C
R
M
)
Z
'
T
+G
v|w= NÑ)'s1,'ZB
BBCmÇB
ZD;Ç_
B7CEÇB
ZD`Ç`
BECBÇ7Cf
ZmÇD
BBCiÇB
ZD;Ç_
ECmÇB
ZDBÇ_
vMw= 5)'sT1,'ZBsKZBU
Z
I*J(%0 QC %:24-3 )-)':*4* ,H .8( *(5,-+ ,2+(2 2).( 5,-*.)-. U* ,H .8( )5(.,>8(-,-(
.2)-*H(2 8:+2,3(-).4,- 4- 4*,>2,>)-,' 5).)':I(+ J: .= M= '= 0 4- .8( >2(*(-5(
,H J)*( ). +4HH(2(-. .(1>(2).02(*C ()5.4,- 5,-+4.4,-* )* 4- !)J'( BC
L !8( +).) H,2 + 4* 346(- H,2 5,1>)24*,- H2,1 ;`
C
.8( QZG( *0J*.4.0.(+ 5,1>'(<(* ) )-+ ' )2( *0>>,*(+':
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
T' (&*)C= ;7BD= 99= BZD k U
&'()*( +, -,. )+/0*. 1)234-*

Dalton Transactions
Page 6 of 11
View Article Online
DOI: 10.1039/C9DT04532E

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 7 of 11
View Article Online
DOI: 10.1039/C9DT04532E
6&(%#.7 ,.80
A23"451
5)--,. J( 4*,').(+= ) *'438. (<5(** ,H J)*( T0> ., BC` (c046U 4* ?P! *.0+: 4- ,02 >2(64,0* 5,-.24J0.4,-C;`
3(-(2)'': 0*(+C "- ,-( 5)*( T5).)':*. +U .8( +FQ)\G?M 2).4, ]8(- .8( .2)-*H(2 8:+2,3(-).4,- 4* 5).)':*(+ J: 5,1>'(< )
[)* 6)24(+ TBFB )-+ BF;U J0. .8( ,J*(26(+ 2).( 5,-*.)-. [)* ,2 ' 4- .8( >2(*(-5( ,H ) J)*(= .8( 2(*.4-3 *.).( 4* .8( 8:+24+(
(**(-.4)'': 4+(-.45)' T7C7E` )-+ 7CB7i 8ZB= 2(*>(5.46(':= ). ;`r#U 5,1>'(< T!) ,2 !'= 2(*>(5.46(':U 2).8(2 .8)- .8( 5).4,-45
!80*= [8(2()* ) H42*. (c046)'(-. ,H J)*( 4* -((+(+ ., )5.46).( 5,1>'(< TSX)Yd ,2 SX'Yd= 2(*>(5.46(':UC QG 1,-4.,24-3 ,H .8(
.= M= 0 )-+ += 4. )>>()2* .8). .8( (<5(** )1,0-. 8)* -, 8:+24+( 5,1>'(< !' 4- .8( >2(*(-5( ,H !&2@\ TB7 (c046U 4- #i?i
(HH(5. ,- .8( 5).)':.45 5:5'(C
4-+45).(* -, 58)-3( T*(( P4302( MBEU= 8(-5( -, *>,-.)-(,0*
>2,.,- .2)-*H(2 [4.8 H,21).4,- ,H S!/OYd [4.8 )- !&2@Z
5,0-.(24,-C A++4.4,- ,H )5(.,>8(-,-( ., .84* *,'0.4,- ). 2,,1
.(1>(2).02( ,-': *8,[(+ .8( *',[ H,21).4,- ,H .8( BZ
>8(-:'(.8)-,' >2,+05. T*(( P4302( M;7U= [4.8,0. )-: 58)-3( H,2
.8( 2(*,-)-5(* ,H !C !84* 1()-* .8). ! 4* )- ,HHZ',,> 2(*.4-3
*.).( 0-+(2 .8(*( 5,-+4.4,-*C
<0= C0)@.#*:$*) '*:)(::*&#H
!8( >,**4J4'4.: ,H
) G((2[4-Z&,--+,2HZO(2'(: TG&OU
1(58)-4*1 5)- J( ()*4': +4*5)2+(+ H,2 .[, 2()*,-*A T!U .8(
5).)':*. [,2N* 0-+(2 J)*(ZH2(( 5,-+4.4,-*= [8(2()* .8( G&O
>).8[):* 2(c042(* )'N,<4+( J4-+4-3 ., .8( 5).)':*.q T!!U .8(*(
5).)':*.* 5)--,. ,HH(2 ) *(5,-+ ,>(- 5,,2+4-).4,- *4.( H,2
5,,2+4-).4,- ,H .8( N(.,-( *0J*.2).( J(5)0*( ,H .8( *.2,-3
58(').4-3 >,[(2 ,H .8( Q&Q '43)-+C !)N4-3 4-., )55,0-. .8( G(Q
8438 J)*454.: 4- .8( Bfg 20.8(-401 5,1>'(<(* [4.8 '43)-+* 4 )-+
;= [( >2,>,*( .8). .8( )5(.,>8(-,-( 8:+2,3(-).4,- 4- -().
4*,>2,>)-,' H,'',[* .8( 5')**45)' Q,:,24 1(58)-4*1B_= 4- [8458
) *410'.)-(,0* .2)-*H(2 ,H .8( 4*,>2,>)-,' 1(.8:-( \ ).,1 .,
.8( 0 ).,1 )-+ ,H .8( @\ >2,.,- ., .8( J)*45 Q ).,1 ,5502*
.82,038 ) >(245:5'45 .2)-*4.4,- *.).( 4- .8( 2).(Z+(.(214-4-3 *.(>
T5:5'( A 4- M58(1( iUC ]( *0>>,*( .8). .8( >2,.,-).(+ 8:+24+(
5,1>'(< S!/OYY 1438. J( .8( .20( 5).)':.45)'': )5.46( *>(54(*=
8)64-3 ) 2(').46(': 8438 (-(23: )-+ .8(2(H,2( J(4-3 >2(*(-. 4-
.8( 5).)':.45 *:*.(1 4- ) ',[ *.).4,-)2: *.).( 5,-5(-.2).4,-C P,2
.8( '(** J)*45 )2:'Z*0J*.4.0.(+ Q&Q *:*.(1*= ,- .8( ,.8(2 8)-+=
)- (<.(2-)' J)*( 4* -(5(**)2: )-+ .8( 2()5.4,- ,5502* 64) 5:5'(
R= 41>'45).4-3 .8( -(0.2)' 8:+24+( 5,1>'(< != )* 6)'4+).(+ J: )
"- ,2+(2 ., 6)'4+).( .84* >2,>,*4.4,-= -([ ?P! 5)'50').4,-*
[(2( 5)224(+ ,0. H,2 .8( >2,>,*(+ 5:5'( AC !8( 2(*0'.*= *8,[- 4-
P4302( i= *033(*. .8). .8( >2,>,*(+ 1(58)-4*1 4* 4-+((+
)55(**4J'(C !8( 5)'50').4,-* [(2( 5)224(+ ,0. ). .8( *)1( '(6('
,H .8(,2: )* .8,*( >2(64,0*': >2(*(-.(+ H,2 5:5'( R T*(( +(.)4'*
4- .8( %<>(241(-.)' *(5.4,-U=;` 0*4-3 .8( H0'' Q&Q '43)-+ )-+ )
J(-I(-( 24-3 ., 1,+(' .8( 2()' )2(-( '43)-+ )-+ 4-5'0+(+
5,22(5.4,-* H,2 *,'6).4,- (HH(5.* J: 0*( ,H ) >,')24I)J'(
5,-.4-001 4- 4*,>2,>)-,' )-+ H,2 +4*>(2*4,- (HH(5.* +024-3
,>.414I).4,-C @-': .8( 5).)':*. )5.46).4,- *.(>= 4-6,'64-3 \;
+('46(2: ., SXYd H2,1 4*,>2,>)-,' ., 3(-(2).( S!/OYd )-+
)5(.,-(= [)* )-)':*(+C !8( (-(23(.45 >2,H4'( ,H .8( *0J*(c0(-.
+('46(2: ,H \; ., )5(.,>8(-,-(= [8458 ,5502* *:11(.245)'': 4-
.8( 2(6(2*( +42(5.4,-= *8,0'+ J( c04.( *414')2C !8( H42*. *.(> ,H
.84* >2,5(** 4* .8( 58',24+( 4,- +4**,54).4,- H2,1 C !, 2(-+(2
.8( 5)'50').(+ 1,+(' 5',*(2 ., 2()'4.:= (<>'454. *,'6).4,- ,H .8(
58',24+( 4,- J: \ZJ,-+4-3 4-.(2)5.4,-* [4.8 .82(( *,'6(-.
L(>IFMN!#/5-N)' OP<:&QR%&S
)GHB
GH3
GHG
1GHI
1>HB
14HI
D>1-EA
D>1-EAJJJ5K2'(>
DBEA
)
DBEAJJJ-5!#/
- !.'7*&1F5;
AE7,>D7
.'7*&1F
@"?*&
I*J(%0 BC P2(( (-(23: >2,H4'( H,2 .8( +4**,54).4,- ,H .8( 1,+(' ST#i\iU 0TQ&QU#'Y 5,1>'(< 4- !&2@\ )-+ H,2 .8( 3(-(2).4,- ,H .8( 5).)':.45)'': )5.46( ST#i\iU 0\TQ&Q\UYd
5,1>'(< TQ&Q n G(Q&&8;QG(UC
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
T' (&*)C= ;7BD= 99= BZD k X
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 8 of 11
View Article Online
DOI: 10.1039/C9DT04532E
A23"451
6&(%#.7 ,.80
1,'(50'(* T1,+(''(+ J: 1(.8)-,'U [(2( 5,-*4+(2(+= :4('+4-3 ) )**43-1(-. ,H .8( 2(*,-)-5(* H,2 .8( 5,1>'(<(* )-+ ! [)*
*'438.': (<,(2345 >2,5(**C !84* 4- )32((1(-. [4.8 .8( J)*(+ ,- .8( )-)':*4* ,H DB&= B\= BD#VB\X= B\ZB\ #@MÜ )-+ B\ZBD#
(<>(241(-.)' (64+(-5( T*(( )J,6(UC !8( 4*,>2,>)-,' 1,'(50'( \Má# QG *>(5.2)C B\= DB& )-+ BD# QG *>(5.2) [(2( ,J.)4-(+
H42*. +,5N* ,-., .8( Q&Q '43)-+ J: (*.)J'4*84-3 )- \ZJ,-+ )* ) ,- R20N(2 A6)-5( D77 )-+ R20N(2 A6)-5(""" _77 *>(5.2,1(.(2*
>2,.,- +,-,2 [4.8 ,-( ,H .8( .[, QG( 32,0>*= :4('+4-3 )-+ 2(H(2(-5(+ ., .8( 2(*4+0)' *43-)'* ,H +(0.(2).(+ *,'6(-. TB\
SXYdsss\@!&2 .82,038 ) *(5,-+ *'438.': (<,(2345 >2,5(**C !8(-= )-+ BD#U= )-+ ., f`p \D&@_ TDB&= (<.(2-)' *.)-+)2+UC #,1>'(<(*
.8( >2,.,- 4* .2)-*H(22(+ ., .8( QG( 32,0> )-+ .8( 1(.8:-( \ STZ\R#iG(iU 0#';Y;=D7 STZiZ#:1U 0#';Y;=DB .8( 414-,>8,*>8,Z
).,1 4* *410'.)-(,0*': .2)-*H(22(+ ., .8( 0 5(-.2( ., J(5,1( -)14-(* A/4=;m
;
)-+ S&8;&TQ\Z Z#i\_#@@%.U;YR2;f [(2(
;E
) 8:+24+( '43)-+ )-+ :4('+ .8( \ZJ,-+(+ )++05. J(.[((- S!/OYd >2(>)2(+ )55,2+4-3 ., +(*524J(+ >2,5(+02(*C
>?#$@0:*: &+ -@!-<,OA%G=<,A%G= <A%G ^ #4BOQ4__1$= <1=H !, )
*0*>(-*4,- ,H S&8;&TQ\A2LU;YR2 TBC;` 3= ;CB7 11,'U 4- J(-I(-(
T_7 1$U= -(). %.;Q\ T7C;_ 1$= ;C; 11,'U [)* )++(+ )-+ .8(
14<.02( [)* *.422(+ H,2 ; 8C !8( >2(54>4.).( [)* H4'.(2(+ ,HH )-+
.8( H4'.2).( [)* (6)>,2).(+ ., +2:-(**C !8( 2(*4+0( [)*
+4**,'6(+ 4- +4(.8:' (.8(2 T;7 1$U )-+ .8( >2,+05. [)*
>2(54>4.).(+ [4.8 8(<)-( T_7 1$UC !8( [84.( 52:*.)''4-(
>2(54>4.).( [)* +24(+ !" -&8%, T:4('+ n BC7i 3= EfpUC A-)'C 5)'5+
H,2 #D7\;EQ;@_&A #= m7CD7q \= `Cm7q Q= `C_mpC P,0-+A #= m7C`Eq
\= `Cfmq Q= `CD_pC DB&VB\X QG T#i?iUA { Z`CDC B| QG T#i?iUA {
fC7B T+= DT|| n fC_= _\= #i\_T#@;%.UU= mCEB T+++= DT\& n B;Cf= DT\\
n fC7= _T\\ n BCf= _\= ,R\&8U= mC;; T+= DT|| n fC_= _\= #i\_T#@;%.UU=
iCEm T1= i\= T*] ^Z\&8U= iC;E T*= B\= Q\U= _C7m Tc= DT\\ n mC;=
_\= #\;#\DU= 7CEE T.= DT\\ n mC;= i\= #\;#\DUC BD#VB\X QG
T#i?iUA { BiiCm T*= #@;%.U= B_`C_ T*= !R#i\_T#@;%.UU= BDBCE T+= ;Tyà
n ECf= _Z#&8U= BDBCf T+= _Tyà n ;Cf= Z#&8U= BDBC; T*= *Z
T>2,.,- +,-,2U )-+ )5(.,-( T>2,.,- )55(>.,2U= 64) ) H42*.Z,2+(2
*)++'( >,4-. T;7CD4 51ZBU ',5).(+ ). ,-': B7Cm N5)'F1,' )J,6( .8(
*.)2.4-3 5,1>'(< )-+ B`Ci N5)'F1,' )J,6( *:*.(1 SXYdsss\@!&2C
A- " # )-)':*4* +(1,-*.2).(* .8). .84* 5,-5(2.(+
>2,.,-F8:+24+( .2)-*H(2 4* c04.( )*:-582,-,0*= .8( >2,.,-
.2)-*H(2 ,550224-3 ,- .8( 0>*',>( H2,1 SXYdsss\@!&2 ., .8( *)++'(
>,4-.= [8(2()* .8( 8:+24+( .2)-*H(2 >2,5(** .)N(* >')5( )2,0-+
.8( *)++'( >,4-.C ?4**,54).4,- ,H .8( \ZJ,-+(+ )++05. :4('+
*(>)2).( S!/OYd )-+ )5(.,-( 4- ) -()2': 4*,(2345 >2,5(**C P4-)'':=
?P! 5)'50').4,-* [(2( 5)224(+ ,0. ., )**(** .8( *.)J4'4.: ,H S!/
OYd [4.8 2(*>(5. ., >2,.,- .2)-*H(2 >2,5(**(* ., (4.8(2 .8(
4*,>2,>,<4+( 4,- ,2 4*,>2,>)-,' T1,+(''(+ J: 1(.8,<4+( )-+
1(.8)-,'= 2(*>(5.46(':UC "- ,2+(2 ., *).4*H)5.,24': 1,+(' .8(
*.2,-3 J)*( 4- .8( )'5,8,' *,'6(-.= .8( \ZJ,-+(+ )++05. [4.8
.82(( *,'6(-. 1,'(50'(*= SG(@TG(@\UDYZ [)* 0*(+= '()+4-3 ., )
TG(@\U_ 5'0*.(2 )-+ .8( -(0.2)' 8:+24+( !C !8( 5)'50').4,-*
:4('+ )- (<,(2345 >2,5(** [4.8 vV4&2@\ n ZiC_ N5)'F1,'= 4-
)32((1(-. [4.8 .8( (<>(241(-.)' ,J*(26).4,- .8). ! 4* *.)J'( 4-
!&2@\ T4- ,.8(2 [,2+*= !&2@\ 4* -,. )J'( ., >2,.,-).( ! )-+
3(-(2).( S!/OYdUC !8(2(H,2(= .8( 5)'50').4,- 5,-H421 .8). ! 4* .8(
#i\_T#@;%.UU= BD7CE T+= BTyà n BDBCE= !Z#&8U= B;fCi T+= DTyà n B;CD=
*Z#&8U= B;;CB TJ2C *= Z#i\_T#@;%.UU= B;7C; T+= DTyà n BfCD= ,Z
#i\_T#@;%.UU= `ECE T*= #\;#\DU= BDCE T*= #\;#\DUC
5).)':*. 2(*.4-3 *.).( [8(- 3(-(2).(+ H2,1 4- .8( >2(*(-5( ,H >?#$@0:*: &+ A<$B/4BC0B=2(47D-@!-<,/ /3&7=<,C0=EF < '=H !, )
) *.2,-3 J)*(C #,-6(2*(':= >2,.,- .2)-*H(2 H2,1 S!/OYd ., .8( *,'0.4,- ,H 414-,>8,*>8,-)14-( ; T7CD; 3= BC77 11,'U 4-
*,'6(-.= 1,+(''(+ J: .8( TG(@\UD 5'0*.(2= ., :4('+ ! )-+ J(-I(-( T`7 1$U ) 7Ci G *,'0.4,- ,H Q)\G?M 4- .,'0(-( TBCf
SG(@\;TG(@\U;Yd 4* 8438': (-+,(2345 TvV4&2@\ n ;BC7 N5)'F1,'UC 1$= BC7f 11,'U [)* )++(+ )-+ .8( 2(*0'.4-3 *,'0.4,- [)*
!84* 1()-* .8). S!/OYd 4* *.)J'(= !')' 4* -,. +(>2,.,-).(+= 4- .8( *.422(+ H,2 ; 8 ). 2,,1 .(1>(2).02(C !8(- *,'4+ ST!iZ
)J*(-5( ,H .8( *.2,-3 J)*(C !80*= )55,2+4-3 ., P4302( i= .8( #iG(iU 0#';Y; T7CD_ 3= 7C`7 11,'U [)* )++(+= )-+ .8( 2()5.4,-
2(*.4-3 *.).( ,H .8( 5).)':*. 4* SXYdC !8( '4N(': 2).(Z+(.(214-4-3 14<.02( [)* *.422(+ ,6(2-438.C !8( 2(*0'.4-3 *,'0.4,- [)*
*.(> 4* .8( 5,-6(2*4,- ,H SXYdsss\@!&2 ., S!/OYdsss@n#G(;= H,2 ) +4'0.(+ [4.8 8(<)-( T`7 1$U= )-+ .8( >2(54>4.).( [)* H4'.(2(+
5)'50').(+ H2(( (-(23: *>)- ,H B`Ci N5)'F1,'C P,2 *:*.(1 '= .8( ,HHC !8( H4'.2).( [)* 5,-5(-.2).(+ ., ` 1$ )-+ .8(- 8(<)-( [)*
(<>(241(-.)'': +(.(214-(+ )5.46).4,- >)2)1(.(2* TvXÖ
n
)++(+ [4.8 *1)'' >,2.4,-* [4.84- 7C` 8 T;7 1$ 4- .,.)'U ., 4-+05(
BECBÇ7Cf N5)'s1,'ZB )-+ v9Ö n ZmÇD 5)'s1,'ZBsKZBU :4('+ ) vVÖ ,H 52:*.)''4I).4,-C !8( >2(54>4.).(+ ,2)-3(Z2(+ 52:*.)'* [(2(
;BC; N5)'F1,' ). ;Ef KC !8( 6)'0( (*.41).(+ J: ?P! 4* (6(- H4'.(2(+ ,HH= [)*8(+ [4.8 8(<)-( T; < ` 1$U )-+ +24(+ 4- 6)5001
',[(2 )-+ 4* .80* c04.( 5,-*4*.(-. [4.8 .8( H()*4J4'4.: ,H .84* T:4('+ n 7C_m 3= mmpUC A-)'C 5)'5+ H,2 #D;\Df#'Q;& 0A #= i;CBfq \=
5,-5(2.(+ >).8[):C !8( 0-+(2(*.41).4,- ,H .8( 5:5'( vVÖ J: iC;7pC P,0-+A #= i;C`_q \= iC`fpC DB&VB\X QG T#i?iUA { `;C7_C
.8( ?P! 5)'50').4,-* 1): J( 2(').(+ ). '()*. 4- >)2. ., .8( *1)'' B| QG T#i?iUA { mCE; T1= _\= `,]_a^Z\&8U= mC;D TJ2C *= D\= `*] ^Z
J(-I(-( 1,+('= [8458 41>,*(* ',[(2 *.(245 5,-*.2)4-.* ,- .8( \&8U= mCB` T++=DT\\ n fC7= _T\& n BC;= ;|= ,Z\!,'U= iCEB T+= DT\\ n fC7=
5,-5(2.(+ .2)-*4.4,- *.).( 2(').46( ., .8( ')23(2 #iG(i 24-3 4- ;\= *Z|!,'U= iCfm TJ2C *= D\= `*] ^aZ\&8U= ;Cm_ T+= DT\& n ;7C7= D\=
*:*.(1 'C "-)5502)54(* 4- .8( *,'6).4,- 1,+(' )-+ 4- .8( G(QU= ;CB_ T*= D\= G(!,'U= BCf; T*= Bf\= #iG(iUC BD#VB\X QG
8)-+'4-3 ,H .8( (-.2,>45 5,-.24J0.4,- 4- .8( 5,-+(-*(+ >8)*( T#i?iUA { B_iC; T+= ;T#& n DC;= !Z#!,'TQUU= BD`CB TJ2C += ;T#& n B7C_= ,Z
5)- )'*, 5,-.24J0.( ., .8( 5,1>0.).4,-)' (22,2C
#&8U= BDBCm TJ2C += ;T#& n B7Ci= ,aZ#&8U= BDBC_ TJ2C *= Z#&8U= BDBC7
TJ2C *= aZ#&8U= B;mCfZB;fC7 T,6(2')>>(+= `*]*a^Z#&8U= B;ECB T*= *Z
#
!,'U= B;mC7 T+= `T#& n BCD= Z#!,'U= B;_Ci T+= DT#& n B7C7= ,Z#!,'U= fECD
1]P0%*80#$.7
T*= #iG(iU= D;Cf T*= G(QU= ;7Cf T*= G(!,'U= BiC7 T*= #iG(iUC
>?#$@0:*: &+ A<$B/ /)?80#0=2(47D-@!-<,/ /4BOQ4__1$=!EF < 0=H
!, ) *0*>(-*4,- ,H 1 T7C_E 3= 7CEi 11,'U 4- J(-I(-( T_7 1$U )
7Ci G *,'0.4,- ,H Q)\G?M 4- .,'0(-( TBCm 1$= BC7; 11,'U [)*
)++(+ )-+ .8( 2(*0'.4-3 *,'0.4,- [)* *.422(+ H,2 B 8 ). 2,,1
.(1>(2).02(C !8(- *,'4+ STÄiZ R5:1(-(U 0#';Y; T7C;E 3= 7C_f
N0#0%.7 P%&)0'(%0:H
A'' 1)-4>0').4,-* [(2( 5)224(+ ,0. 0*4-3 *.)-+)2+ M58'(-N
.(58-4c0(* 0-+(2 )- ).1,*>8(2( ,H +2: )23,-C M,'6(-.* [(2(
>024H4(+ J: *.)-+)2+ 1(.8,+* )-+ +4*.4''(+ >24,2 ., 0*(C !8(
\ k T' (&*)C= ;7B;= 99= BZD
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 9 of 11
View Article Online
DOI: 10.1039/C9DT04532E
6&(%#.7 ,.80
A23"451
11,'U [)* )++(+= )-+ .8( 2()5.4,- 14<.02( [)* *.422(+ T1= D\= `*] ^Z\&8U= iCf; T.= DT\\ n iCf= B\= aZ\&8U= iCm_ T.+=DT\\
,6(2-438.C !8( >2(54>4.).( [)* H4'.(2(+ ,HH= .8( H4'.2).( [)* mC_= _T\& n ;C_= ;\= *aZ\&8U= iCim T+= DT\\ n fC_= _\= #i\_T#@;%.UU=
n
D
D
(6)>,2).(+ ., ` 1$ )-+ .8(- +4'0.(+ [4.8 D7 1$ ,H %.;@C !8( _CfB T+= T\\ n `Ci= ;\= #i\_T#:1UU= _Cm_ T+= T\\ n iC7= ;\=
D
D
,2)-3( 52:*.)''4-( >2(54>4.).( [)* H4'.(2(+ ,HH )-+ [)*8(+ [4.8 #i\_T#:1UU= _CBD Tc= T\\ n iCi= _\= #\;#\DU= ;C`_ T*(>.= T\\
D
n
%.;@ TD<` 1$U= .8(- +24(+ !" -&8%, T:4('+ n 7CiE 3= ffpUC A-)'C iCf= B\= #\G(;U= BCff T*= D\= G(5:1U= BC;D T+= T\\ n iCf= i\=
D
5)'5+ H,2 #_7\_;#'Q;@_& 0A #= iBC_;q \= `C_BpC P,0-+A #= iBC``q #\G(;U= BC7B T.= T\\ n iCi= i\= #\;#\DU= Z;CEf T*= B\= 0\UC
;
\= `C`_pC DB&VB\X QG T#i?iUA { _mC;C B| QG T#i?iUA { fCB; T++= BD#VB\X QG T#i?iUA { BiiCm T*= #@;%.U= B`iC7 T+= T#& n iCD= !Z
;
_
DT\\ n fCf= `T\& n 7Cf= _\= #i\_T#@;%.UU= mCEf T+++= DT\& n B;C_= DT\\ #QT#@;%.UU= BD;Cf T+= T#& n B7C7= ,Z#&8U= BD;Ci T+= T#& n DC7= R
n fC;= _T\\ n BC_= ;\= ,Z\&8U= mCfm T+++= DT\& n B;C7= DT\\ n fC;= _T\\ #&8U= BD;C` T+= BT#& n E_Ci= !Z#&8U= BD;C` T+= _T#& n ;C`= aZ#&8U= BD;C_
n BC_= ;\= ,aZ\&8U= mC;D T.+= DT\\ n mC;= _T\& n BCi= B\= Z\&8U= mCBE T+= ;T#& n B7Cf= ,aZ#&8U= BD7Ci T*= *Z#i\_T#@;%.UU= B;ECD T+= DT#&
n
T.+= DT\\ n mC;= _T\& n ;Cf= _T\\ n BCi= ;\= *Z\&8U= mCBD T++= DT\\
n
BBCE= *Z#&8U= B;mCE T+= BT#& n B7DC`= !aZ#&8U= B;fCf T+= DT#& n BBCf=
D
D
fCf= _T\& n 7Cf= _\= #i\_T#@;%.UU= iCmi T.+= T\\ n mCi= _T\& n BCi= *aZ#&8U= B;BCE T+= T#& n B;CD= ,Z#i\_T#@;%.UU= BBECi T*= Z
B\= WZ\&8U= iCiE T.+= DT\\ n mCi= _T\& n ;Cf= ;\= *WZ\&8U= _CEf T+= #i\_T#@;%.UU= B7mC; T*= !Z##:1U= B7BCB T*= !aZ##:1U= fBC; T*= #\#:1U=
D
DT\\ n iC7= ;\= #i\_T#:1UU= _Cf; T+= T\\ n iC7= ;\= #i\_T#:1UU= miCB T*= #\#:1U= i7C7 T*= #\;#\DU= D;Cm T*= #\G(;U= ;DCE T*=
D
D
_CBm Tc= T\\ n mC;= _\= #\;#\DU= ;Cim T*(>.= T\\ n iCf= B\= #\G(;U= BECf T*= G(#:1U= B_C` T*= #\;#\DUC
#\G(;U= BCiE T*= D\= G(5:1U= BC7_ T.= DT\\ n mC;= i\= #\;#\DU= 7CE` A7$0%#.$*Z0 80$@&' &+ J0#0%.$*&# &+ !)H !, ) *,'0.4,- ,H )
T+= DT\\ n iCf= i\= #\G(;UC BD#VB\X QG Tyi?iUA{ BiiC` T*= #@;%.U= T7C7BB 3= 7C7;7 11,'U 4- #i?i T7Ci 1$U= Q)%.DR\ TBC7 G 4-
;
B
B`DCm T+= T#& n `C_= !Z#QT#@;%.UU= BD`Cf T+= T#& n BBiCi= !WZ#&8U= .,'0(-(= ;7 x$= 7C7;7 11,'U [)* )++(+= .8( 2(*0'.4-3 14<.02(
BD_Cf T+= ;T#& n BBCD= ,aZ#&8U= BDDCD T+= BT#& n EECD= !Z#&8U= BDDC7 T+= [)* *8)N(- H,2 ` 14- ). 2,,1 .(1>(2).02( )-+ )-)':I(+ J:
_T#& n ;Cm= aZ#&8U= BD;Ci T+= _T#& n ;C`= Z#&8U= BD;C_ T+= ;T#& n B7CE= DBàVB\X QG C A55,2+4-3 ., DB&VB\X QG T#i?iU= .8( 5,-.(-. ,H !)
D
,Z#&8U= BD7CE T*= *Z#i\_T#@;%.UU= B;ECB T+= T#& n B;CB= *Z#&8U= TY& _ECf= Y Z_CB;U )H.(2 ;7 14- [)* 5)C m7p )-+ 4. 32)+0)'':
0\
B;fCi T+= DT#& n B;CD= *aZ#&8U= B;;C; T+= DT#& n B;C;= ,Z#i\_T#@;%.UU= +(52()*(+ [4.8 .41(C
B;7Ci T*= Z#i\_T#@;%.UU= B7_CB T*= !Z##:1U= E`Cm T*= !Z##:1U= fBCB T*= 4.$.7?$*) :$('*0:H "- ) .:>45)' (<>(241(-.= .8( >2(5).)':*. T7C7;
#\#:1U= mfCE T*= #\#:1U= i7CB T*= #\;#\DU= DBC` T*= #\G(;U= ;;C_ 11,'U [)* *0*>(-+(+ 4- !&2@\ T` 1$U )-+ .8(- .2().(+ T4H
T*= #\G(;U= BfCi T*= G(#:1U= B_C` T*= #\;#\DUC
)>>2,>24).(U [4.8 ) 7Ci G *,'0.4,- ,H Q)\G?M 4- .,'0(-( TBZBC`
%& '(!) J0#0%.$*&# &+ A<$B/.%0#0=2(O<,-,=F <!=H N0#0%.7 (c046CUC "- .8( >2(*(-5( ,H J)*(= .8( 14<.02( [)* >2('414-)2:
P%&)0'(%0H !8( 8:+24+( 5,1>'(<(* ! [(2( 3(-(2).(+ !" #!$% 4- *.422(+ H,2 `ZB;7 14-0.(* T!)J'( BU= .8(- 4. [)* [)21(+ ). .8(
) QG .0J(C !, ) *,'0.4,- ,H .8( 58',24+( 5,1>'(< T7C7;7 +(*42(+ .(1>(2).02( H,'',[(+ J: .8( )++4.4,- ,H +,+(5)-( TB
11,'U 4- #i?i T7Ci 1$U )-+ 4*,>2,>)-,' T7C;7 11,'= B7 x$U= ) 11,'= 7C;;` 1'U )-+ )5(.,>8(-,-( T; 11,'= 7C;DD 1'UC
Q)\G?M *,'0.4,- T;C7 G 4- !\P= B` x$= 7C7D 11,'= BC` (c046CU A'4c0,.* T7CB 1$U [(2( +4'0.(+ [4.8 +4(.8:' (.8(2 T7Cf 1$U )-+
[)* )++(+C !8( 2(*0'.4-3 *0*>(-*4,- [)* 643,2,0*': *.422(+ H,2 H4'.(2(+ .82,038 ) *4'45) J(+C !8( 2()5.4,- *)1>'(* [(2(
` 14- ). 2,,1 .(1>(2).02( ., 5,1>'(.( .8( +4**,'0.4,- ,H )-+ )-)':*(+ J: u# (c04>>(+ [4.8 9ä] u# #,'01- [4.8 ) ?RZBGM
.8(- .8( 2()5.4,- [)* H,'',[(+ J: QG C
*.).4,-)2: >8)*( T>2,32)1A ;` 14- ). `7 ã#= [4.8 H02.8(2 8().4-3
#,1>'(< !R [)* 3(-(2).(+ H2,1 . T7C7B_ 3= 7C7;7 11,'U )-+ 2).( ;7 ã# F 14- ., Bm7 ã#q 2(.(-.4,- .41(*A bT)5(.,>8(-,-(U n
Q)\G?M T7C7D7 11,'U 4- E`p )H.(2 ; 8C DBàVB\X QG T#i?iUA { ;_ 14-= bTBZ>8(-:'(.8)-,'U n ;` 14-= bT+,+(5)-(U n DB 14-UC
DBCEC B\ QG T#i?iUA { fC;` T1= ;\= ,R\&8U= mC_D T1= ;\= ,aR\&8U= a/%.? )%?:$.77&J%.P@?H M4-3'( 52:*.)'* ,H '= 0 [(2( ,J.)4-(+
mC;E T1= D\= T*d ^Z\&8U= iCmD T1= D\= T*d ^aZ\&8U= iCf; T+= DT||
fCf= _\= yi\_T!,'UU= iCmE T+= DTââ n EC;= _\= yi\_T!,'UU= ;C7m T*= i\= 5,''(5.4,-* [(2( >(2H,21(+ ,-
n
J: *',[ +4HH0*4,- ,H 8(<)-( 4-., J(-I(-( *,'0.4,-*C !8( +).)
)
R20N(2 A&%h ?z@
G(!,'U= BCE` T*= Bf\= #iG(iU= ZDCD7 T 0\UC BD#VB\X QG T#i?iUA { +4HH2)5.,1(.(2 (c04>>(+ [4.8 )- A>(< "" ##? +(.(5.,2= 0*4-3
B_mC` T+= ;T#& n DCf= !Z#!,'TQUU= BDfCf T+= BT#& n B7BCD= !Z#&8U= BDDC; #,Kå 2)+4).4,- Tç n BC`_Bmf oU H,2 0 )-+ G,Kå 2)+4).4,- Tç n
T+= ;T#& n fCi= ,aZ#&8U= BD;Cm T+= ;Tyà n B7Ci= ,Z#&8U= BDBCi T+= _Tyà
n
7CmB7mD oU H,2 'C P2)1(* [(2( 4-.(32).(+ 0*4-3 .8( R20N(2
_
B
;Cm= Z#&8U= BDBCB T+= Tyà n ;Ci= aZ#&8U= BD7C` T+= T#& n mmCD= !WZ MA"Q! *,H.[)2( >)5N)3(D; J: ) -)22,[ZH2)1( )'3,24.81C A
#&8U= B;fCf T*= *Z#!,'U= B;fCi T+= DTyà n BBCm= *Z#&8U= B;fC; T+= *aZ *(14(1>4245)' )J*,2>.4,- 5,22(5.4,- [)* )>>'4(+ [4.8 .8(
#&8U= B;mC7 T+= `Tyà n ;CD= Z#!,'U= B;`CE T+= DTyà n EC;= ,Z#!,'U= E7CB !]"QARM T 0U ,2 .8( MA?ARMDD T 'U >2,32)1* 0*4-3 .8(
T*= #iG(iU= ;7Cm T*= G(!,'U= BmC; T*= #iG(iUC
4-.(-*4.: +).) ,H (c046)'(-. 2(H'(5.4,-*C !8( *.205.02(* [(2(
A-)',3,0*':= H2,1 ' T7C7B; 3= 7C7BE 11,'U )-+ Q)\G?M *,'6(+ [4.8 .8( +0)'Z*>)5( 1(.8,+ [4.8 M\%$h!D_ )-+ 2(H4-(+
T7C7;f 11,'U 5,1>'(< !' [)* 3(-(2).(+ 4- i`p :4('+ )H.(2 B 8C J: .8( H0''Z1).24< '()*.Z*c0)2(* .(58-4c0( )3)4-*. P; 4-
8N'
DBàVB\X QG T#i?iUA { _BCDC B\ QG T#i?iUA { mCEf T1= ;\= ,R\&8U= )-4*,.2,>45 )>>2,<41).4,- [4.8 .8( M\%$h$D` *,H.[)2( >)5N)3(C
mC`E T1= ;\= _aR\&8U= mC;` TJ2C *= D\= `*] ^R\&8U= iCE; TJ2C *= D\= !8( >,*4.4,-* ,H .8( 8:+2,3(- ).,1* [(2( 5)'50').(+= )-+ )''
`*] ^aR\&8U=iCfD T+= DT\\ n f= ;\= ,Zyi\_T!,'UU= iCmf T+= DT\\ n mCi= 8:+2,3(- ).,1* [(2( 2(H4-(+ 0*4-3 .8( 24+4-3 1,+(' [4.8
D
;\= *Ryi|_T!,'UU= ;C`; T+= T\& n ;7C_= D\= G(TQUU= ;C7f T*= D\= BC`z(cT#1U )-+ BC;z(cT#4U= [8(2( z(cT#1U )-+ BC;z(cT#4U )2(
G(!,'U= ;C7D T*= Bf\= G(#:1U= ZDCm; T*= B\= 0\UC
2(*>(5.46(': .8( (c046)'(-. .8(21)' >)2)1(.(2* ,H 1(.8:' )-+
A-)',3,0*':= H2,1 0 T7C7BB 3= 7C7B_ 11,'U )-+ Q)\G?M )'' ,.8(2 5)2J,- ).,1* ., [8458 5,22(*>,-+4-3 \ ).,1* )2(
T7C7B_ 11,'U 5,1>'(< !0 [)* 3(-(2).(+ 4- E;p :4('+ )H.(2 ; 8C J,-+(+C !8( 52:*.)'* ,H 0 [(2( .[4-* ,H 2(').46(': >,,2 c0)'4.:q
DBàVB\X QG T#i?iUA { DfC_C B\ QG T#i?iUA { fC7E T+++= DT\&
n
.8( 1)<41)' )584(6(+ +).) 5,1>'(.(-(** [)* ,-': fDC;p 0> .,
D
_
D
B;C7= T\\ n fC7= T\\ n BCi= ;\= ,R\&8U= fC77 T+= T\\ n fC_= _\= .8( 2(*,'0.4,- ,H 7CfDD oC \,[(6(2= +0( ., .8( 8438
D
D
#i\_T#@;%.UU= mC_f T++= T\& n BBC;= T\\ n mCi= ;\= ,aR\&8U= mC;_ +).)F>)2)1(.(2* 2).4, T~ B7U )-+ 2(').46(': ',[ 2(*4+0)'* [( +,
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
T' (&*)C= ;7BD= 99= BZD k `
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 10 of 11
View Article Online
DOI: 10.1039/C9DT04532E
A23"451
6&(%#.7 ,.80
-,. 8)6( +,0J.* )J,0. .8( 5,22(5.-(** ,H .84* 52:*.)' *.205.02(C H,2 >2(5,,2+4-).4,- ,H .8( N(.,-( ., H,21 ) >(245:5'45 .2)-*4.4,-
?(.)4'(+ 52:*.)'',32)>845 4-H,21).4,- 4* 346(- 4- !)J'( MDC *.).( *414')2': ., .8( >2,>,*(+ ,-( H,2 Q,:,24Z"N)24:) 5).)':*.*C
#2:*.)'',32)>845 +).) 8)6( J((- +(>,*4.(+ ., .8( #)1J24+3( P2,1 .8( >2)5.45)' >,4-. ,H 64([= .8( 1)/,2 )+6)-.)3( ,H 0*4-3
#2:*.)'',32)>845 ?).) #(-.2(= ##?# -01J(2* BE`if;mZ QZ1(.8:').(+ 0Q&Q 5).)':*.* 0-+(2 J)*(ZH2(( 5,-+4.4,-* 4*
BE`if;fC #,>4(* ,H .8( +).) 5)- J( ,J.)4-(+ H2(( ,H 58)23( 64) .8( ',-3Z.(21 STA2(-(U 0TQ&QUYd *.)J4'4.: ., >2,.,-,':*4* [4.8
8..>AFF[[[C55+5C5)1C)5C0NF+).)é2(c0(*.F54H= ,2 J: (Z1)4'4-3 4*,>2,>)-,'= [8458 *((1* ., J( .8( 5).)':*. 1)4- +(32)+).4,-
+).)é2(c0(*.É55+5C5)1C)5C0N= ,2 J: 5,-.)5.4-3 !8( #)1J24+3( >).8[):= (*>(54)'': ). ('(6).(+ .(1>(2).02(*C
#2:*.)'',32)>845 ?).) #(-.2(= B; z-4,- ,)+= #)1J24+3( #R;
B%è= zKq H)<A d__T7UB;;DZDDi7DDC
4&#+7*)$: &+ *#$0%0:$
4&8P($.$*&#.7 ;0$.*7:C !8( 5)'50').4,-* [(2( 5)224(+ ,0. 0*4-3
.8( u)0**4)- 7E >2,32)1 >)5N)3(Di [4.84- .8( ?P! )>>2,)58
0*4-3 .8( Em? H0-5.4,-)'=Dm [8458 41>'454.': 4-5'0+(* ) +4*>(2*4,-
5,22(5.4,-C !8( J)*4* *(. 5,1>24*(+ .8( $AQ$;?è J)*4* *(.=
!8(2( )2( -, 5,-H'45.* ., +(5')2(C
[8458 4-5'0+(* )- %#& )-+ )031(-.(+ [4.8 )- H >,')24I).4,-
A)b#&c70'J080#$:
H0-5.4,- Tå n BC;D`UDf H,2 .8( 0 ).,1= )-+ .8( *.)-+)2+ iZ
!84* [,2N [)* *0>>,2.(+ J: 0**4)- M54(-5( P,0-+).4,- T32)-.
DBBuT+=>UDE J)*4* *(.* H,2 )'' ,.8(2 ).,1*C !8( *,'6).4,- (HH(5.
Q,C BEZBDZ77_`EUC M>(5.2)' 58)2)5.(24I).4,-= ('(1(-.)' )-)':*4*
[)* 4-5'0+(+ +024-3 ,>.414I).4,- J: 0*( ,H .8( MG? >,')24*)J'(
[(2( >(2H,21(+ [4.8 .8( H4-)-54)' *0>>,2. H2,1 G4-4*.2: ,H
5,-.4-001 4- 4*,>2,>)-,' Tê n BE=;i_UC !8(21,58(145)'
M54(-5( )-+ \438(2 %+05).4,- ,H .8( 0**4)- P(+(2).4,- 0*4-3
5,22(5.4,-* [(2( ,J.)4-(+ ). ;EfCB` K ,- .8( J)*4* ,H H2(c0(-5:
.8( (c04>1(-. ,H #(-.(2 H,2 1,'(50')2 5,1>,*4.4,- *.0+4(* ,H
5)'50').4,-*= 0*4-3 .8( *.)-+)2+ )>>2,<41).4,-* T4+()' 3)*= 2434+
"Q%@M AMC ]( )'*, .8)-N .8( P2(-58 aG4-4*.ë2( +(* AHH)42(*
2,.,2 )-+ 8)21,-45 ,*54'').,2UC A H02.8(2 5,22(5.4,- ,H BCE`
%.2)-3ë2(*b H,2 ) &8C?C H('',[*84> ., "MM )-+ .8( #A$G"&
K5)'F1,' [)* )>>'4(+ ., J24-3 .8( u 6)'0(* H2,1 .8( 3)* >8)*(
1(*,5(-.(2 ,H .8( z-46(2*4.: ,H !,0',0*( H,2 ) 32)-. ,H
TB ).1U ., .8( *,'0.4,- TB 1,'F$U *.)-+)2+ *.).(C_7
5,1>0.).4,-)' .41(C
4&#)7(:*&#:
,&$0: .#' %0+0%0#)0:
]4.8 .84* *.0+: [( 8)6( +(1,-*.2).(+ .8( (HH(5. ,H .8( Q=&Z
*0J*.4.0(-.* 4- .8( Q&Q '43)-+ )-+ .8( )2(-( -).02( ,- .8(
B
F, !8# !" 012&",*)$&33!8 4C)*!#$1+P c!/%"8$!,"&3 ?,3)8%3&1
4&$&3+#!#= !C "N)24:) )-+ GC %C M84J)*)N4= T%+*CU= M>24-3(2A
R(2'4-= ;7BB= 6,'C DmC
>(2H,21)-5( ,H .8( TA2(-(U 0TQ&QU 5,1>'(<(* 4-
)5(.,>8(-,-( .2)-*H(2 8:+2,3(-).4,- 5).)':*4*C ]( 8)6(
+4*5,6(2(+ .8). .8( QZ).,1* J)*454.: 4* .8( H().02( .8). +(H4-(*
J,.8 .8( 1(58)-4*1 ,H .8( ,0.(2Z*>8(2( 8:+2,3(- .2)-*H(2 .,
N(.,-(= (4.8(2 4-6,'64-3 Q&Q '43)-+Z)**4*.)-5( ,2 [4.8,0. .84*
>2(5,,2+4-).4,- *.(>= )-+ .8( 5,-+4.4,-* ). [8458 .8( 5).)':*.
5)- ,>(2).(C
;
D
_
?C ])-3 )-+ ?C A*.205= 4C)*' 7)-'= ;7B`= U= ii;BZiifiC
hC ]0= #C ])-3 )-+ 9C h4),= G3&$!"' ?)$' 7)-'= ;7B7= UQ= DZBEC
MC \)*8430584= AC P0/44= 9C !)N(8)2)= !C "N)24:) )-+ C Q,:,24= T'
A*' 4C)*' 9,8'= BEE`= X= m`i;Zm`iDC
`
9C !)N(8)2)= MC \)*8430584= AC P0/44= MCZ4C "-,0(= !C "N)24:) )-+ C
Q,:,24= 4C)*' 4,**%"'= BEEi= ;DDZ;D_C
i
m
KC G02).) )-+ !C "N)24:)= T' 012' 4C)*'= BEEE= BQ= ;BfiZ;BfmC
!C "N)24:) )-+ AC 9C R')5N(2= A88,%"$# 4C)*' 7)#'= ;77m= Q9=
BD77ZBD7fC
"C G)*).,= MC Ü0/4= ]C AN42) )-+ "C !)N),= 9+"3)$$= ;77E= 9=
Bi;BZBi;iC
!C !,03(= !C \)N)1).)= \C Q)2)= !C K,J):)*84= QC M):,= !C M)4.,=
ÜC K):)N4 )-+ !C "N)24:)= T' A*' 4C)*' 9,8'= ;7BB= KK= B_Ei7Z
B_EiDC
z-+(2 J)*45 5,-+4.4,-*= [8(- .8( >2(5).)':*. 4* 5,-6(2.(+
4-., .8( )5.46( 20.8(-401 8:+24+( *>(54(*= .8( '(** *.(245)'':
(-501J(24-3 Z5:1(-( '43)-+ )-+ .8( 1,2( ('(5.2,-Z+,-).4-3
QZ*0J*.4.0(-.* H)6,02 .8( 5).)':*. )5.464.:= )'.8,038 J,.8
+(52()*( .8( *.)J4'4.: ,H .8( 5).)':.45)'': )5.46( 8:+24+( *>(54(*=
+0( ., (4.8(2 *4+( 2()22)-3(1(-. ., Big Ä`Z5:5',8(<)+4(-:'
5,1>'(<(*;` ,2 H)54'( >2,.,-).4,- ,H .8( QZ).,1* H,'',[4-3 J:
.8( Q&Q '43)-+ +(5,,2+4-).4,-= 2(*>(5.46(':C (>')5(1(-. ,H
.8( &Z>8(-:' 32,0>* [4.8 (.8:' *0J*.4.0(-.* 8)* '4..'( (HH(5. ,-
.8( 5).)':*. >(2H,21)-5(= [84'( 4.* *.)J4'4.: *0HH(2* *43-4H45)-.':
J(5)0*( ,H .8( Q&Q '43)-+ +(32)+).4,- +0( ., 5,-5022(-. &ZQ
J,-+ J2()N4-3 [4.8 )'N,<4+(Z4,-C "- 3(-(2)'= >2('414-)2:
3(-(2).4,- ,H .8( )5.46( 0\ *>(54(* *.2,-3': '414.* .8( ,6(2)''
*.)J4'4.: ,H .8( 5).)':.45 *:*.(1 1)N4-3 4. 6(2: *(-*4.46( ., .8(
c0)'4.: ,H .8( *,'6(-. )-+ .8( .(1>(2).02(C
f
E
B7 &C AC ?0J= AC G).*0-)14= MC K0[).) )-+ ÜC K):)N4= T' A*'
4C)*' 9,8'= ;7BE= Q = ;iiBZ;immC
BB C \,+3N4-*,-= OC 90254N= AC è)-,..4Zu(2,*)= \CuC Q(++(-= AC
R')5N)J:= uC9C #')2N*,- )-+ GC ]4''*= 012&",*)$&33!8#= ;7B_=
KK= ``BmZ``;_C
B; C Q,:,24 )-+ MC \)*8430584= A88,%"$# 4C)*' 7)#'= BEEm= K9=
EmZB7;C
BD GC 9C &)'1(2 )-+ GC ]4''*= F)$1&C)51,"RA#+**)$1= BEEE= 9=
;7_`Z;7iBC
B_ GC Ü)1)N)[)= \C "., )-+ C Q,:,24= T' A*' 4C)*' 9,8'= ;777=
!!= B_iiZB_mfC
B` #C &C #)*(: )-+ 9C RC 9,8-*,-= T' 012' 4C)*'= ;77D= B\= BEEfZ
;77BC
Bi !C K,4N( )-+ !C "N)24:)= A5-' 9+"$C' 4&$&3'= ;77_= KQB= DmZ_BC
Bm 9C MC GC M)1(5= 9C %C R)5N6)''= &C uC A-+(2**,- )-+ &C R2)-+.=
4C)*' 9,8' 7)-'= ;77i= KU= ;DmZ;_fC
Bf $C 9C \,0-/(.= GC 9C P(230*,- )-+ GC #,[4(= 012&",*)$&33!8#=
;7BB= K9= _B7fZ_BB_C
!8( 0*( ,H J)*( 4* -,. -(5(**)2: H,2 .8( 5,1>'(<(* [4.8
J)*45 QZG( 32,0>*= [8458 4* ) 2)2( ,55022(-5( 4- .2)-*H(2
8:+2,3(-).4,- 5).)':*4*q [4.8,0. J)*( .8(*( >2(5).)':*.* )2(
)'*, 8438': )5.46( )-+ *43-4H45)-.': 1,2( *.)J'(C ]4.8 .8( 8('> ,H
N4-(.45 )-)':*(* )-+ ?P! 5)'50').4,-* [( 8)6( *033(*.(+ )-
)'.(2-).46( 1(58)-4*1 ,H .2)-*H(2 8:+2,3(-).4,- 0-+(2 J)*(Z
H2(( 5,-+4.4,-*= [8458 4-6,'6(* )**4*.)-5( ,H .8( J)*45 QZ).,1
9 k T' (&*)C= ;7B;= 99= BZD
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
&'()*( +, -,. )+/0*. 1)234-*

&'()*( +, -,. )+/0*. 1)234-*
Dalton Transactions
Page 11 of 11
View Article Online
DOI: 10.1039/C9DT04532E
6&(%#.7 ,.80
A23"451
BE ]C ]C QC @= AC 9C $,038 )-+ C \C G,224*= 012&",*)$&33!8#=
;7BB= K9= B;DiZB;`;C
;7 &C AC ?0J )-+ !C "N)24:)= T' A*' 4C)*' 9,8'= ;7BD= KU= ;i7_Z
;iBEC
;B &C AC ?0J )-+ 9C #C u,2+,-= S&3$," F1&"#'= ;7Bi= QU= im`iZ
imfBC
;; &C AC ?0J )-+ 9C #C u,2+,-= A49 4&$&3+#!#= ;7Bm= X= iiD`Zii``C
;D 9CZ]C \)-+32))H )-+ %C 9C G(4/(2= T' A*' 4C)*' 9,8'= ;77m= !`=
D7EEZDB7D
;_ AC &)6',6) )-+ %C 9C G(4/(2= 4C)*GC+#4C)*= ;7B;= K= D_E;Z
D_EiC
;` "C MC M4-,>)'-4N,6)= !C AC &(3)-,6)= QC OC R('N,6)= %C ?(:+4(2=
9C #C ?)2)-= %C MC M80J4-)= AC GC K)'*4- )-+ C &,'4= O%1' T' .",12'
4C)*'= ;7Bf= !9 \= ;;f`Z;;EEC
;i "C MC M4-,>)'-4N,6)= !C AC &(3)-,6)= OC OC Q,64N,6= "C OC
P(+:)-4-= @C AC P4'4>>,6= QC OC R('N,6)= %C MC M80J4-)= C &,'4
)-+ AC GC K)'*4-= 4C)*' O%1' T'= ;7Bm= !K= B`_;_ZB`_D`C
;m !C AC &(3)-,6)= "C MC M4-,>)'-4N,6)= AC MC &(2(30+,6= "C OC
P(+:)-4-= AC ?(1,-5()0= QC AC z*.:-:0N )-+ AC GC K)'*4-=
S&3$," F1&"#'= ;7Bi= QU= Bm7D7ZBm7_BC
;f @C OC u0*(6= !C AC &(3)-,6)= AC OC u,-58)2= &C OC &(.2,6*N44= KC
AC $:**(-N, )-+ QC AC z*.:-:0N= GC,# C,1%# 9%3/%1= ;77E= \Q=
D;;ZDDBC
;E !C AC &(3)-,6) )-+ AC GC K)'*4-= 9+"$C)#!#= )55(>.(+C ?@"A
B7CB7``F*Z77DEZBiE7;_;C
D7 GC R(--(..= !C QC \0)-3= !C G).8(*,-= AC M14.8= MC "..(' )-+
]C Q45N(2*,-= .",12' 9+"'= BEf;= ! = m_ZmfC
DB MC RC 9(-*(-= MC 9C ,+3(2 )-+ GC ?C M>45(2= T' 012&",*)$'
4C)*'= BEEf= UUB= B`BZB`fC
D; MA"Q! 6fCD_AC= R20N(2 AhM= G)+4*,-= ]4*5,-*4-= zMA= ;7BDC
DD $C K2)0*(= C \(2J*.Z"21(2= uC GC M8('+245N )-+ ?C M.)'N(= T'
A 3' 41+#$&33,21'= ;7B`= Q\= DZB7C
D_ uC M8('+245N= A8$& 41+#$&33,21' A= ;7B`= X = DZfC
D` uC GC M8('+245N= A8$& 41+#$&33,21' 4= ;7B`= 4X = DZfC
Di GC 9C P24*58= uC ]C !205N*= \C RC M58'(3('= uC %C M50*(24)= GC AC
,JJ= 9C C #8((*(1)-= uC M5)'1)-4= OC R)2,-(= RC G(--0554=
uC AC &(.(2**,-= \C Q)N).*0/4= GC #)245).,= hC $4= \C &C
\2).584)-= AC PC "I1):',6= 9C R',4-,= uC è8(-3= 9C $C M,--(-J(23=
GC \)+)= GC %8)2)= KC !,:,.)= C P0N0+)= 9C \)*(3)[)= GC
"*84+)= !C Q)N)/41)= ÜC \,-+)= @C K4.),= \C Q)N)4= !C O2(6(-= 9C
9C AC G,-.3,1(2:= 9C %C &(2)'.)= PC @3'4)2,= GC R()2>)2N= 9C 9C
\(:+= %C R2,.8(2*= KC QC K0+4-= OC QC M.)2,6(2,6= C K,J):)*84=
9C Q,21)-+= KC )38)6)58)24= AC (-+(''= 9C #C R02)-.= MC MC
":(-3)2= 9C !,1)*4= GC #,**4= QC (3)= 9C GC G4'')1= GC K'(-(=
9C %C K-,<= 9C RC #2,**= OC R)NN(-= #C A+)1,= 9C 9)2)14'',= C
u,1>(2.*= C %C M.2).1)--= @C Ü)I:(6= AC 9C A0*.4-= C #)114=
#C &,1(''4= 9C ]C @58.(2*N4= C $C G)2.4-= KC G,2,N01)= OC uC
è)N2I([*N4= uC AC O,.8= &C M)'6)+,2= 9C 9C ?)--(-J(23= MC
?)>>2458= AC ?C ?)-4('*= íC P)2N)*= 9C RC P,2(*1)-= 9C OC @2.4I= 9C
#4,*',[*N4 )-+ ?C 9C P,<= V&%##!&" H> `V&%##!&"6 ."8'6
d&33!"2/,15 4F6 :HH>^C
Dm MC u2411(= T' 4,* ' 4C)*= ;77i= !X= BmfmZBmEEC
Df AC ]C %8'(2*= GC R,(81(= MC ?)>>2458= AC u,JJ4= AC \,(''[)2.8=
OC 9,-)*= KC PC K,(8'(2= C M.(31)--= AC O('+N)1> )-+ uC
P2(-N4-3= 4C)*' GC+#' B)$$'= BEED= !9\= BBBZBB_C
DE C K24*8-)-= 9C MC R4-N'(:= C M((3(2 )-+ 9C AC &,>'(= T' 4C)1"'
GC+#'= BEf7= X!= i`7Zi`_C
_7 OC MC R2:)-.*(6= GC MC ?4)'', )-+ ]C AC u,++)2+= """= T' GC+#'
4C)*' c= ;77f= != Em7EZEmBEC
!84* /,02-)' 4* l !8( ,:)' M,54(.: ,H #8(14*.2: ;7<<
T' (&*)C= ;7BD= 99= BZD k
&'()*( +, -,. )+/0*. 1)234-*