.E=9L=(<H(GHM(9<CNLM(F9K@BGL(
Dalton Transactions
Page 8 of 9
DOI: 10.1039/C8DT01573B
F-/&!(#(
'?DA>2<(*2=6(
jqX(
jrX(
kiX(
6X(+X(2NU(1X(+9GHA9KU(!X((9@HM9(9G<(+X(8A=G@U(*1CDA5U(kiirU(
XZTU(kni\knlX(
!X( ,BLAU( (X\7X( &P9G@U( (X( "HB@( 9G<( 0X( (X( ,B;AHE9LU( *1CDA5!
*1>?C538JU(kiipU(VU(omi\omoX(
(X(7X(&P9G@U(!X(,BLAU((X("HB@U(1X("HNO=GU(!X(5X(!A=GU(*X(!X(
!A=G(9G<(0X((X(,B;AHE9LU(&J!/=J!!85=J!-?3JU(kiiqU(UWTU(lnml\
lnnlX(
+X(1X(!KGHE<U(!X(!X(%K==GU((X($X(&NEO9MU(1X('X(1MNII(9G<(+X(!X(
&=KL9FU(*1CDA5!*1>?C538JU(kiioU(UU(oi\onX(
&X( *BNU( "X( ,BLAB<=U( 2X( 29G9D9( 9G<( &X( )9M9NK9U( *1CDA5!
!?==D>JU(kijjU(VU(lirX(
'X(.H;AHKHOLDBU(&X(59G@U( (X('X( $=E<:ERNFU( 6X( 8A9G@U( !X( *X(
!GM9KBL(9G<(8X( 9HU(&J!/=J!!85=J!-?3JU(kijnU(UW[U(mlkq\mlljX(
$X( 2HLABFBMLN( 9G<( ,X( ,9D9LABF9U( -39J! ,5@?ACBU( kijnU( YU(
jqiooX(
$X(2HLABFBMLN(9G<(,X(,9D9LABF9U(*1CDA5!!?==D>JU(kijmU(YU(
nimjX(
&X(-S9P9U()X()HL9D9U(2X()BM9U()X(7HLABD9P9(9G<(+X(&9@9U(
!85=J!#DAJ!&JU(kijoU(VVU(onpn\onqkX(
0X(.X(1BC:=LF9U($X(&X( =BC=KU(*X( KNGLO=E<U( X((X( X($HEF=KU((X(
&X()X()X(&BKL;A:=K@U(0X($X(+X(*9G@=U((X()X(*X(*HP=(9G<(#X(5X(
+=BC=KU(-395>35U(jrrpU(V[\U(joij\joimX(
1X(&X(+X(1HGMC=GLU(0X(.X(1BC:=LF9U(+X(&X(.X(O9G(%=G<=K=G(
9G<(#X(5X(+=BC=KU(&J!/=J!!85=J!-?3JU(kiiiU(UVVU(pmqp\pmrlX(
+X()X(2L=U(1X( AHKU(+X()E9PHGGU(%X(!GBEDNF9KU(&X((X((B9HU(!X(
"H:E=KU( !X( 1I9GG=G:=K@U( 5X( +9@=KE=BGU( &X( &N@E( 9G<( +X(
=EE=KU(!85=J!#DAJ!!&JU(kiioU(UVU(jqnn\jqpmX(
$X(&X( =BC=KU(0X(.X(1BC:=LF9U(&X()HHBCF9GU(!X(*X(1I=D(9G<(#X(
5X(+=BC=KU(&J!/=J!!85=J!-?3JU(jrrqU(UVTU(opoj\oporX(
&X(-S9P9U(2X($NCB@9R9U(7X(,BB<HF=U(,X(&HMM9U(+X($NCBDB(9G<(
,X(,9D9LABF9U(&J!/=J!!85=J!-?3JU(kijjU(UWWU(konj\konpX(
+X($X('LE9FU(#X(0HC9LU("X(+X( =K@=RU(!X(2X((HAGLHG(9G<(!X(%X(
7H<AU(*1>?!(5CCJU(kiilU(WU(kor\kplX(
6X(6B9HFBG@U(+X(&9@9U(2X(+9MLNFNK9\'GHN=U(7X(0NU(!X(5X(
!<<BLHG(9G<()X()9GHU( &J!!85=J!-?3J!"1<C?>!.A1>BJU(jrrlU(
kmppX(
2X(+9K9G@HGB(9G<("X( HGB>9SBU(*1>?B31<5U(kijlU(YU(qqlp\
qqnjX(
!X(,9D9FNK9U(2X()HR9F9U(7X(+BR9M9(9G<(&X(1ABGHA9K9U(&J!
+8FBJ!!85=J!!U(kijoU(UVTU(momp\monkX(
)X(&N9G@U(!X(19A9U()X("BKB9GU(!X(+X((B9G@U(.X(*X(#X(!ANU((X(+X(
2HNKU( "X( +X( %NE<B( 9G<( !X( !X( +9KMBU( *1>?B31<5U( kijoU( \U(
jlmqq\jlmrpX(
9<LHK:=<(&\:HG<=<()M0,H(^+(x($=U(0N_(;HFIE=Q=L(<BL9II=9K=<X(
$NKMA=KFHK=U( >KHF( MA=( AHFH@=G=HNLER( <BLI=KL=<( LHENMBHG( H>(
MA=( )M0,HZ15,2( ^+( x( $=U( 0N_( ;HFIHLBM=( LHENMBHGU( :NG<E=<(
15,2L(IK=;BIBM9M=<(NIHG(9<<BMBHG(H>(MKB>ENHKH9;=MB;(9;B<X(2ABL(
K=LNEM( BG<B;9M=L( MA9M( MA=( >HKF9MBHG( H>( &\:HG<=<( F=M9EEH\
LNIK9FHE=;NE9K( IHERF=KL( IE9RL( 9G( BFIHKM9GM( KHE=( >HK( MA=(
LHEN:BEBS9MBHG(H>(15,2LX(((
kjX(
kkX(
klX(
kmX(
knX(
koX(
kpX(
(!?>7<:4CB(?7(:>C6A6BC(
2A=K=(9K=(GH(;HG>EB;ML(H>(BGM=K=LM(MH(:=(<=;E9K=<X(
F4;>?F<6586=6>CB(
2ABL( PHKD( P9L( LNIIHKM=<( :R( +#62Z(1.1( )!)#,&'( @K9GML(
jo)inplk(9G<((.jp&inlql(^!HHK<BG9MBHG(!LRFF=MKR_U(9(!ANH(
3GBO=KLBMR( (HBGM( 0=L=9K;A( %K9GMU( 9G<( MA=( 1;B=G;=( 0=L=9K;A(
.KHFHMBHG( $NG<( >KHF( MA=( .KHFHMBHG( 9G<( +NMN9E( !B<(
!HKIHK9MBHG(>HK(.KBO9M=(1;AHHEL(H>((9I9GX(5=(9;DGHPE=<@=("KX(
+9L9MHN('LABA9K9( 9G<( "KX( 7NDB(-DB@9P9(^,9MBHG9E('GLMBMNM=(H>(
!<O9G;=<( 'G<NLMKB9E( 1;B=G;=( 9G<( 2=;AGHEH@R( ^!'12__( >HK( MA=BK(
LNIIHKM(K=@9K<BG@(MA=(F=9LNK=F=GM(H>(MA=(09F9G(LI=;MK9X(
kqX(
krX(
-676A6>46B(
liX(
ljX(
lkX(
llX(
jX(
kX(
lX(
mX(
nX(
oX(
pX(
qX(
rX(
jiX(
!X($HNJN=RU((X(+X(*=AG(9G<(!X(+X(*=O=ENMU(/4EJ!)1C5AJU(jrriU(
VU(knm\knpX(
$X(&X( =BC=KU(0X(.X(1BC:=LF9U(&X()HBCF9GU(!X(*X(1I=D(9G<(#X(5X(
+=BC=KU(&J!/=J!!85=J!-?3JU(jrrqU(UVTU(opoj(\(oporX(
-X((X(%X(+X(%HHKU(1X('X(1X(&=G<KBDL=U(.X(7X(5X("9GD=KL(9G<(#X(
5X(+=BC=KU(!85=J!-?3J!,5EJU(kijpU(XZU(ookj(\(oolpX(
&X\/X(.=G@U((X\$X(6NU(7X\8X(!A=GU(*X\8X(5NU(!X\&X(2NG@(9G<(/X\
8X(79G@U(!85=J!!?==D>JU(kijmU(YTU(jllm\jllpX(
&X(&H>F=B=KU(0X(&HH@=G:HHFU(+X(#X(*X(5HNM=KL(9G<(3X(1X(
1;AN:=KMU(&J!/=J!!85=J!-?3JU(kiinU(UV[U(krjl(\(krkjX(
*X( KNGLO=E<U( X((X( X($HEF=KU(#X(5X(+=BC=K(9G<(0X(.X(1BC:=LF9U(
!85=J!,5EJU(kiijU(UTUU(mipj\mirpX(
lmX(
lnX(
loX(
*X(*X(79G@U(6X(6X(29GU(8X(/X(59G@(9G<(6X(8A9G@U(!85=J!,5EJU(
kijnU(UUYU(pjro\pklrX(
2X($X(!X(<=(%K==>(9G<(#X(5X(+=BC=KU(*1CDA5U(kiiqU(XYWU(jpj\
lpX(
&X()9M9NK9U(7X()NF9S9P9U(7X(+9GBP9U('X(3F=SNU(1X(1NSNDBU(7X(
-AMLND9(9G<(7X(!;AB:9U(-F>C85C93!)5CJU(jrrrU(UTWU(knnn\
knnqX(
jplX(
6X(8X(79GU($X(59G@U( X(8A=G@(9G<($X(&X(&N9G@U(!85=J!-?3J!
,5EJU(kijkU(XUU(oimk\oionX(
+X( NKGPHKMAU(*X(+X(29G@U((X(0X()NFI>=KU(!X((X("NG;9GU($X(*X(
=R=KU(%X(*X($BHK=U(1X((X(0HP9G(9G<(!X(5=<=KU(*1CDA5U(kijjU(
X[VU(llm\llpX(
(
(
(
(
(
(
(
(
jjX(
jkX(
jlX(
jmX(
$X( &=K:LMU( "X( "HAE=KU( .X( +B;A9=E( 9G<( 5X( &X( BG<=KU(
)13A?=?<J!,1@94!!?==JU(kijlU(WXU(kil\kkiX(
(X( X( =;D(9G<(1X((X(0HP9GU(&J!/=J!!85=J!-?3JU(kiilU(UVYU(
jlrkk\jlrklX(
$X(1X(&9GU(+X(&B@N;AB(9G<("X(%X()NKMAU(/4EJ!)1C5AJU(kiipU(U]U(
lrkq\lrljX(
!X(5BGM=K(9G<(3X(1X(1;AN:=KMU(!85=J!-?3J!,5EJU(kijoU(XYU(
nljj\nlnpX(
jnX(
joX(
/X(!9H(9G<((X(!X(0H@=KLU(/4EJ!)1C5AJU(kiirU(VUU(kr\nlX(
4X(1@H::9(9G<("X(+X(%NE<BU(!85=J!-?3J!,5EJU(kiirU(W\U(jon\
jqmX(
jpX(
!X(59G@U()X(29D=BU(2X(29D9A9LAB(9G<(!X((9O=RU(!85=J!-?3J!
,5EJU(kijlU(XVU(knrk\koirX(
\([(&J!*1=5XU(kijkU(TTU(j\l(
2ABL(CHNKG9E(BL(d(2A=(0HR9E(1H;B=MR(H>(!A=FBLMKR(kiQQ(
.E=9L=(<H(GHM(9<CNLM(F9K@BGL(