Synthesis and characterisation of cobalt and nickel compounds with phosphinothiol ligands. Crystal and molecular structures of [Co{ {2- (Ph2P)-6- (Me3Si)C6H3S)} }3], [Ni{ {2- (Ph2P)-6- (Me<

Article abstract of DOI:10.1016/S0277-5387(98)00252-6

Theelectrochemical oxidation of anodic metal (cobalt or nickel) in an acetonitrile solution of phosphinothiol ligands, 2- (Ph₂P)C₆H₄SH, 2- (Ph₂P)-6- (SiMe₃)C₆H₃SH, 2- (Ph₂

Full text of DOI:10.1016/S0277-5387(98)00252-6

Polyhedron Vol[ 06\ Nos[ 14\ 15\ pp[ 3346Ð3353\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] SS9166!4276"87#99143!X
Synthesis and characterisation of cobalt and
nickel compounds with phosphinothiol ligands[
Crystal and molecular structures of
ðCo"1!"Ph1P#!5!"Me2Si#C5H2S##2Ł\
ðNi"1!"Ph1P#!5!"Me2Si#C5H2S##1Ł and
ðCo"1!"Ph1PO#!5!"Me2Si#C5H2S#1Ł
P[ Perez!Lourido\a J[ Romero\a\ꢁ J[ A[ Garc(a!Vazquez\a\ A[ Sousa\a
ꢀ
ꢀ
ꢀ
J[ Zubietab and K[ Marescab
aDepartamento de Qu(mica Inorganica\ Universidad de Santiago de Compostela\
ꢀ
04695 Santiago de Compostela\ Spain
bDepartment of Chemistry\ Syracuse University\ Syracuse\ NY 02133\ U[S[A[
"Received 13 April 0887^ accepted 07 June 0887#
Abstract*The electrochemical oxidation of anodic metal "cobalt or nickel# in an acetonitrile solution of
phosphinothiol ligands\ 1!"Ph1P#C5H3SH\ 1!"Ph1P#!5!"SiMe2#C5H2SH\ 1!"Ph1PO#!5!"SiMe2#C5H2SH\ a}ords
ðCo"1!"Ph1P#C5H3S##2Ł 0\ ðNi"1!"Ph1P#C5H3S#1Ł 1\ ðCo"1!"Ph1P#!5!"SiMe2#C5H2S#2Ł 2\ ðNi"1!"Ph1P#!5!"SiMe2#
C5H2S#1Ł 3\ ðCo"1!"Ph1PO#!5!"SiMe2#C5H2S#1Ł 4\ ðCo"1!"Ph1PO#!5!"SiMe2#C5H2S#2Ł 5 and ðNi"1!"Ph1PO#!5!
"SiMe2#C5H2S#1Ł 6[ All compounds have been characterised by microanalysis\ IR\ UV!visible\ FAB and NMR
spectroscopic studies and compounds 2\ 3 and 4 by single!crystal X!ray di}raction[ Þ 0887 Elsevier Science
Ltd[ All rights reserved
Keywords] electrochemical synthesis^ crystals structures^ cobalt and nickel complexes^ phosphinothiol com!
plexes
———————————————————————————————————————————————
INTRODUCTION
However\ ligands containing both phosphorus and
sulfur as donor atoms have received far less attention[
In the last decade\ compounds containing aren!
ophosphinothiolate ligands have been reported by
Dilworth and Zubieta\ mainly with heavier transition
metals\ such as molybdenum ð5Ł\ technetium and rhe!
nium ð6Ł\ rhodium ð7Ł and iridium ð8Ł[
As a result of our continuing interest in the chem!
istry of monomeric and low molecularity thiolate com!
plexes\ we now describe the synthesis of cobalt and
nickel compounds with aromatic phosphinothiol
ligands\ using an electrochemical procedure\ where
the metal is the anode of a cell containing the ligand
in an acetonitrile solution[ This method has been suc!
cessfully used for the synthesis of cobalt and nickel
thiolate compounds ð09Ł^ and also for metallic com!
pounds with other ligands having weak acid groups\
Interest in the coordination chemistry of metalÐ
sulfur complexes arises from their potential relevance
to active sites in metallo!enzymes and also from their
ability to adopt various nuclearities and signi_cant
structural complexity ð0Ð3Ł[ These features are the
result of the tendency of thiolate ligands to bridge
metal centres to give polymeric species[ Such associ!
ation phenomena can be controlled by introducing
coligands[ In this context\ the synthesis and charac!
terisation of mixed complexes containing both thi!
olate and additional donors\ such as tertiary
phosphines\ have been objects of extensive studies ð4Ł[
ꢁ Author to whom correspondence should be addressed[
3346

3347
P[ Perez!Lourido et al[
ꢀ
such as heterocyclic thiones ð00Ð03Ł[ Although the 0985"m#\ 639"s#\ 582"s#\ 429"s#[ FAB "m:z#] 533\
compounds ðNi"1!"Ph1P#C5H3S#1Ł and ðNi"1!"Ph1PO#! ðNi"RÐPS#1Ł¦^ 241\ ðNi"RÐPS#Ł¦^ 183\ ðRPÐSŁ¦[ 0H
5!"SiMe2#C5H2S#1Ł have been previously prepared by "CDCl2\ ppm#] d 6[8Ð5[6"m\ 17 H#[ 20P NMR "CDCl2\
nonelectrochemical methods and their structures ppm#] d 43[9[
described ð04Ł\ the other compounds reported in this
article have not been reported previously[
ðCo"1!"Ph1P#!5!"Me2Si#C5H2S#2Ł\ 2[ A solution of
acetonitrile "49 cm2# containing 1!diphenylphosphino!
5!trimethylsilylbenzenethiol "9[296 g\ 9[728 mmol#
was electrolyzed at 09 mA during 0[4 h and 06 mg of
cobalt metal were dissolved from the anode\
Efꢂ9[40 mol F−0[ Dark blue crystals of 2\ suitable
for X!ray studies\ were obtained and the end of the
reaction[ They were recovered by _ltration\ washed
with acetonitrile and dried "9[31 g\ 77)# and identi_ed
EXPERIMENTAL
All manipulations were carried out under an inert
atmosphere of dry nitrogen[ Cobalt and nickel "Ald!
rich Chemie# were used as plates "ca[ 1×1 cm#[
Ligands were synthesised using slight modi_cations
of the standard literature procedure ð05Ł[
by
elemental
analysis[
Anal[
Calc[
for
C52H55CoP2S2Si2] C\ 55[9^ H\ 4[6^ S\ 7\2[ Found] C\
54[4^ H\ 4[8^ S\ 7[9) IR"KBr\ cm−0#] 0443"m#\
0372"m#\ 0323"m#\ 0244"s#\ 0134"m#\ 0975"m#\ 741"s#\
635"s#\ 581"s#\ 429"s#[ FAB "m:z#] 0042\ ðCo"RÐ
Electrochemical synthesis
The electrochemical method used in the synthesis PS#2Ł¦^ 678\ ðCo"RÐPS#1Ł¦^ 254\ ðRPÐSŁ¦[ 0H NMR
of the complexes was similar to that described by Tuck "CDCl2\ ppm#] d 6[6Ð4[8 "m\ 28H#\ 9[09"s\ 8H#\ 9[29
ð06Ł[ The foil anode was suspended from a platinum "s\ 8H#\ 9[49"s\ 8H#[ 20P NMR "CDCl2\ ppm#] d 34[9\
wire and the cathode was also a platinum wire[ The 32[9 and 28[9[
ligand was dissolved in acetonitrile and about 09 mg
ðNi"1!"Ph1P#!5!"Me2Si#C5H2S#1Ł\ 3[ A similar
of tetramethylammonium perchlorate was added to experiment "5 V\ 09 mA\ 1[9 h# with 9[18 g
the solution[ Applied voltages of 09Ð19 V allowed "9[681 mmol# of the ligand 1!"Ph1PO#!5!"Me2Si#
su.cient current ~ow for smooth dissolution of the C5H2SH in 49 cm2 of acetonitrile\ dissolved 10 mg of
metal[ During electrolysis\ nitrogen was bubbled nickel\ Efꢂ9[37 mol F−0[ Green crystals\ suitable for
through the solution to provide an inert atmosphere X!ray studies\ were obtained directly from the cell[
and to stir the solution phase[ The cell can be sum! The solid was collected\ washed with cool acetonitrile\
marised as Pt"−#:CH2CN¦RPÐSH:M"¦#\ where RPÐ diethyl ether and dried under vacuum "9[16 g\ 75)#[
SH represents the ligand and M is either Co or Ni[
Anal[ Calc[ for C31H33NiP1S1Si1] C\ 52[8^ H\ 4[7^ S\
ðCo"1!"PPh1#C5H3S#2Ł\ 0[ Electrochemical oxi! 7[0[ Found] C\ 52[6^ H\ 4[6^ S\ 6[7)[ IR"KBr\ cm−0#]
dation of a cobalt anode in a solution of 1!diphenyl! 0444"m#\ 0371"m#\ 0322"m#\ 0248"s#\ 0132"m#\
phosphinobenzenethiol\ 1!"Ph1P#C5H3SH\ "9[129 g\ 0987"m#\ 741"s#\ 635"m#\ 589"m#\ 439"s#[#[ FAB "m:z#]
9[671 mmol# in acetonitrile "49 cm2#\ at 05 V and 09 678\ ðNi"RÐPS#1Ł¦^ 313\ ðNi"RÐPS#Ł¦^ 254\ ðRPÐSŁ¦[
mA for two h caused 10 mg of cobalt to be dissolved\ 0H RMN "CDCl2\ ppm#] d 6[8Ð5[8"m\ 15 H#\ 9[14"s\
Efꢂ9[37 mol F−0[ During the electrolysis hydrogen 07H#[ 20P NMR"CDCl2\ ppm#] d 41[4[
was evolved at the cathode and at the end of the
ðCo"1!"Ph1PO#!5!"Me2Si#C5H2S#1Ł\ 4 and ðCo"1!
electrolysis green crystalline needles appeared at the "Ph1PO#!5!"Me2Si#C5H2S#2Ł\ 5[ The electrochemical
bottom of the vessel[ The solid was _ltered\ washed oxidation of cobalt in a solution of 1!"Ph1PO#!5!
with acetonitrile and ether and dried under vacuum\ "Me2Si#C5H2SH "9[317 g 0[01 mmol# in acetonitrile
"9[19 g\ 72)#[ Anal[ Calc[ for C43H31CoP2S2] C\ 58[0^ "59 ml# for 2 h at 09 V and 09 mA resulted in the loss
H\ 3[4^ S\ 09[1[ Found] C\ 57[7^ H\ 3[5^ S\ 8[7) IR of 21 mg of cobalt from the anode\ Efꢂ9[49 mol F−0
[
"KBr\ cm−0#] 0460"m#\ 0371"m#\ 0322"s#\ 0305"m#\ During the electrolysis a small amount of a red crys!
0130"s#\ 0980"m#\ 627"s#\ 581"s#\ 414"s#[ FAB "m:z#] talline compound\ 4\ was recovered in the cell as a
828\ ðCo"RÐPS#2Ł¦^ 534\ ðCo"RÐPS#1Ł¦^ 183\ ðRPÐSŁ¦[ minor product[ This compound has been charac!
0H NMR "CDCl2 ppm#] d 7[9Ð5[0 "m\ 31 H#[ 20P terised as ðCo"1!"Ph1PO#!5!"Me2Si#C5H2S#1Ł[ Anal[
NMR "CDCl2\ ppm#] d 39[5\ 27[7 and 26[9[
Calc[ for C31H33P1O1S1Si1Co] C\ 50[3^ H\ 4[3^ S\ 6[7[
ðNi"1!"PPh1#C4H3S#1Ł\ 1[ A similar experiment Found] C\ 50[9^ H\ 4[2^ S\ 6[6)[ Concentration of the
"01 V\ 09 mA\ 1 h# with nickel as anode and 9[119 g solution yielded dark blue crystals "9[24 g\ 65)# of 5[
"9[637 mmol# of 1!"Ph1P#C5H3SH in 49 cm2 of ace! "Anal[ Calc[ for C52H55P2O2S2Si2Co] C\ 51[8^ H\ 4[4^
tonitrile\ dissolved 12 mg of nickel\ Efꢂ9[41 mol F−0
[
S\ 7[9[ Found] C\ 51[4^ H\ 4[3^ S\ 6[8)\ IR"KBr\
As the reaction proceeds\ the solution colour changed cm−0#] 0443"m#\ 0326"s#\ 0241"s#\ 0132"m#\ 0016"s#\
from colourless to dark green[ At the end of the elec! 0951"s#\ 741"s#\ 649"s#\ 580"m#\ 447"s#[ FAB "m:z#]
trolysis the green crystals deposited in the cell were 0190\ ðCo"RÐPS#2Ł¦^ 710\ ðCo"RÐPS#1Ł¦^ 271\ ðRPÐ
recovered\ washed with cool acetonitrile and diethyl SŁ¦[ 0H NMR "CDCl2\ ppm#] d 7[9Ð5[4"m\ 28H#\
ether\ dried under vacuum and identi_ed as 1 "9[06 g\ 9[24"s\ 16H#[ 20P"CDCl2\ ppm#] d 30[6 ppm[
69)#[ Anal[ Calc[ for C25H17NiP1S1] C\ 56[9^ H\ 3[2^
ðNi"1!"Ph1PO#!5!"Me2Si#C5H2S#1Ł\ 6[ Electrolysis
S\ 8[8[ Found] C\ 55[6^ H\ 3[2^ S\ 8[3)[ IR "KBr\ of an acetonitrile solution "49 cm2# containing 1!
cm−0#] 0457"m#\ 0370"m#\ 0326"s#\ 0312"m#\ 0133"s#\ "Ph1PO#!5!"Me2Si#C5H2SH "9[103 g\ 9[45 mmol# using

Synthesis and characterisation of cobalt and nickel compounds with phosphinothiol ligands
3348
09 mA electric current for 0[4 h caused the dissolution yield\ for the synthesis of complexes of cobalt and
of 05 mg of nickel "Efꢂ9[38 mol F−0#[ Concentration nickel with phosphinothiol ligands and the method
of the _nal solution produced green crystals "9[06 g\ represents a simple alternative to other standard
63)# of 6[ Anal[ Calc[ for C31H33P1O1S1Si1Ni] C\ 50[3^ chemical procedures[
H\ 4[3^ S\ 6[7[ Found] C\ 50[9^ H\ 4[2^ S\ 6[6)[
The nickel compounds have general formulae
IR"KBr\ cm−0#] 0445"m#\ 0326"s#\ 0241"s#\ 0133"m#\ ðNi"RPÐS#1Ł where RPÐS stands for the monoanion
0018"s#\ 0956"s#\ 743"s#\ 638"s#\ 581"m#\ 444"s#[#[ FAB of the RPÐSH ligand[ The electrochemical e.ciency
"m:z#] 708\ ðNi"RÐPS#1Ł¦^ 328\ ðNi"RÐPS#Ł¦^ 271\ value\ Ef\ de_ned as the amount of metal dissolved
ðRPÐSŁ¦[ 0H NMR "CDCl2\ ppm#] d 7[5Ð5[3"m\ 15H#\ per Faraday of charge\ was always close to
9[4 "s\ 07H#[ 20P"CDCl2\ ppm#] d 47[1 ppm[
9[4 mol F−0[ This fact and the evolution of hydrogen
at the cathode are compatible with the following reac!
tion mechanisms
Instrumentation
cathode] 1 RP−SH¦1e−:1 RP−S−¦H1
anode]Ni¦1 RP−S−:ðNi"RP−S#1Ł¦1e−[
Elemental analysis were performed on a Carlo!Erba
EA microanalyser[ IR spectra were recorded in KBr
mulls on a Bruker IFS 55 V spectrophotometer[ FAB
mass spectra were recorded on a Kratos!MS!49T con!
nected to a DS89 data system\ using 2!nitrobenzyl
alcohol "2!NBA# a matrix material[ 0H and 20P NMR
spectra were recorded on a Bruker AMX 299 MHz
instrument\ using in all cases CDCl2 as solvent^ 0H
NMR chemical shifts were determined against TMS
as internal standard and 20P NMR against 74)
H2PO3[ Solid!state electronic spectra were recorded
on a Shimadzu UV 2090 PC[
Values of Ef close to 9[4 mol F−0 were found in the
synthesis of cobalt complexes and are indicative of a
similar anodic oxidation mechanism[ However\ the
ddformulation of these compounds is ðCo"RPÐS#2Ł[
This observation suggests an additional oxidation in
solution of Co"II# to Co"III#[ This behaviour has been
previously observed in the synthesis of other cobalt
complexes via an electrochemical procedure ð10Ł[
When the ligand used was 1!"Ph1PO#!5!"SiMe2#
C5H2SH\ in addition to the analogous Co"III#
compound\ a small amount of crystals of ðCo"1!
Ph1P"O#!5!"Me2Si#C5H2S#1Ł could be isolated as a
minor product[
X!ray crystallo`raphy
Compound 2 was studied on a Siemens Smart
di}ractometer\ 3 on a CAD!3 system and 4 on a
Rigaku AFC5S di}ractometer[ Data collection was
carried out under ambient conditions\ using graphite
monocromated Mo Ka for all compounds[ The crystal
parameters and other experimental details of the data
collection are summarized in Table 1[ A complete
description of the details of the crystallographic
methods is given in Table 0[ The structures were solved
by direct methods and re_ned by a full matrix least
squares procedure[ Neutral atom scattering factors
were taken from Cromer and Waber ð07Ł and anom!
alous dispersion were taking from Cromer ð08Ł[ All
calculation were performed using SHELXTL PLUS
"PC version# ð19Ł for 2 and 4 and using DECMic!
roVAX 2499 computer for 3[ No anomalies were enco!
untered in the re_nements of any of the structures[
The crystal parameters and other experimental details
of data collection and re_nement are summarized in
Table 0[ Atomic positions\ a full list of bond lengths\
angles and other crystallographic data have been
deposited as supplementary publication No[ CCDC
091958Ð091960[ Copies can be obtained through
Cambridge crystallographic data centre\ Union Road\
Cambridge[
Structure of ðCo"1!"Ph1P#!5!"Me2Si#C5H2S#2Ł\ 2
Figure 0 shows the molecular structure of 2 together
with the atom labelling scheme[ Selected bond dis!
tances and angles are given in Table 1[ The compound
consists of discrete molecules with the metal coor!
dinated to three monoanionic bidentate ligands\
bonded to the cobalt through their phosphorus and
sulfur atoms[ The environment around the metal can
be described as ðCoP2S2Ł slightly distorted octahedral
geometry^ all the dihedral angles between the coor!
dination planes de_ned by four donors atoms are close
to 89>[ Angles de_ned by two trans donor atoms and
the metal atom are the range 056[56"6#Ð066[28"6#> and
the angles determined by cobalt atom and two cis
donor atoms are close to 89>\ even those cor!
responding to _ve membered chelating rings exhibit
values of 75[38"5#\ 77[26"5# and 70[61"5#>[ These
values are larger than those found in other trischelate
metal complexes containing this ligand[
The arrangement of the three sulfur and phos!
phorous atoms in 2\ is such that the compound can
be described as the meridional isomer[ This is the dis!
position found in ðTc"1!"Ph1P#C5H3S#2Ł\ ðRe"1!
"Ph1P#C5H3S#2Ł ð6Ł and ðIr"1!"Ph1P#C5H3S#2Ł ð8Ł[ 0H
and 20P NMR data "vide infra# show that this arrange!
ment is maintained in solution[
RESULTS AND DISCUSSION
The analytical data show that the electrochemical
procedure described can be satisfactorily used\ in good 1[224"1# A\ with the longer one corresponding to the
The CoÐS bond distances are in the range 1[134"1#Ð
Ä

3359
P[ Perez!Lourido et al[
ꢀ
Table 0[ Crystal data\ data collection and structure re_nement for compounds "2#\ "3# and "4#
"2#
"3#
"4#
Crystal data
Empirical formula
Formula weight
Crystal size "mm#
Crystal system
Space group
C52H55CoP2S2Si2
0044[34
9[04×9[01×9[09
monoclinic
P10:n
aꢂ19[2066"01#
bꢂ01[4522"6#
cꢂ14[714"1#
bꢂ098[467"0#
5100[9"5#
3
C31H33NiP1S1Si1
678[61
9[06×9[04×9[09
monoclinic
P10:c
02[151"2#
01[589"2#
01[762"2#
097[85"2#
1937[8"7#
1
C31H33CoO1P1S1Si1
710[83
39×9[39×9[39
monoclinic
Cc
06[7792"1#
05[6234"2#
18[0760"5#
81[072"0#
7616[9"2#
7
Ä
Unit cell dimensions "A#
Ä
"A#
Ä
"A#
">#
2
Ä
Volume "A #
Z
Dc "g:cm2#
0[125
9[438
1313
0[179
9[639
717
0[140
9[549
2321
Absorption coe.cient "mm−0
F"999#
#
Data collection
Radiation
Temperature "K#
u range ">#
Ä
Mo Ka"9[60962 A#
182"1#
0[00Ð17[21
182"1#
187"1#
0[51Ð11[36
−03³h³01
−02³k³9
9³l³02
0[39Ð17[23
−12³h³12
−11³k³11
−03³l³27
15274
Limiting indices
−16³h³03
−05³k³05
−22³l³23
25700
Re~ections collected
1860
Independent re~ections
03412 "rintꢂ9[969#
689 "rintꢂ9[9057#
02552 "rintꢂ9[9270#
Solution and re_nement
System used
full!matrix least squares on F1
Data:restrains:parameters
R
03412:9:542
9[0992
9[0442
0[270
0[644
689:9:113
9[9234
9[9234
0[042
9[119
−9[100
02550:1:808
9[9492
9[957
0[007
9[147
Rw
Goodness!of!_t on F1
−2
Ä
Ä
Largest di}erence peak "e A
Largest di}erence hole "e A
#
−2
#
−9[228
−9[153
cobaltÐsulfur bond trans to a phosphorous atom\ sug! numbering scheme adopted[ Selected bond distances
gesting some trans in~uence of the phosphorus[ This and angles are given in Table 2[ The structure shows
e}ect has been also observed in other complexes\ such the nickel atom\ located at a crystallographic inver!
as ðIr"1!"Ph1P#C5H3S#2Ł[ Nevertheless\ the average sion centre and coordinated to two thiolato sulfur
Ä
value for the CoÐS bond distances\ 1[175"1# A\ is com! atoms and to two phosphorous atoms of two sym!
Ä
parable to the value of 1[16 A reported for CoÐS bond metry related moieties[ The arrangement is strictly
distances in ðCo"III#ÐS5Ł octahedral complexes ð11Ł or planar to within experimental accuracy\ with the sul!
Ä
1[186"3# A in the octahedral cation ðCo"SC5H4#1 fur atoms in a trans disposition^ bond angles between
"phen#1Ł¦ ð09Ł[ The CoÐP bond distances are also the adjacent atoms are very close to the theoretical
di}erent\ with longer bond distances associated with 89> limit[ The structure of this molecule is similar to
atoms trans to one another[ This may be again due to that of ðNi"1!"Ph1P#C5H3S#1Ł which exhibits the same
the trans in~uence of two mutually trans positioned environment for the metal\ but distinct from that of
phosphine donor atoms[ The average value\ ðNi"1!"Ph1PO#!5!"SiMe2#C5H2S#1Ł which possesses
Ä
1[167"1# A\ is in the range of other octahedral Co"III# planar S1O1 environment around the metal\ in which
complexes containing tertiary phosphine as donors the two thiolate sulfur atoms adopt a cis disposition
Ä
ð12Ł "and references cited therein#[
ð04Ł[ The NiÐS bond distance\ 1[040"2# A\ is similar to
Ä
the value found in ðNi"1!"Ph1P#C5H3S#1Ł\ 1[079"0# A
and also in the range 1[038Ð1[068 A described for
Ä
Structure of ðNi"1!"Ph1P#!5!"Me2Si#C5H2S#1Ł\ 3
Ni"II# square planar complexes with _ve ring chel!
ating ligands and sulfur thiolate donor atoms ð04Ł[
Ä
The molecular structure of ðNi"1!"Ph1P#!5!"Me2Si# In addition\ the NiÐP bond distance\ 1[061"2# A\ is
C5H2S#1Ł is shown in Fig[ 1\ together with the atomic marginally shorter than the value of 1[070"1# A found
Ä

Synthesis and characterisation of cobalt and nickel compounds with phosphinothiol ligands
3350
Fig[ 0[ The molecular structure of ðCo"1!"Ph1P#!5!"Me2Si#C5H2S#2Ł[
Ä
Table 1[ Selected bond lengths "A# and angles "># for ðCo"1!"Ph1P#!5!
"Me2Si#C5H2S#2Ł 2
Co"0#ÐS"1#
Co"0#ÐP"0#
Co"0#ÐP"2#
S"0#ÐC"1#
S"2#ÐC"33#
P"0#ÐC"6#
P"1#ÐC"23#
P"1#ÐC"11#
P"2#ÐC"38#
1[134"1#
1[160"1#
1[291"1#
0[646"5#
0[651"5#
0[732"5#
0[732"5#
0[719"5#
0[716"5#
Co"0#ÐP"1#
Co"0#ÐS"0#
Co"0#ÐS"2#
S"1#ÐC"12#
P"0#ÐC"02#
P"0#ÐC"0#
P"1#ÐC"17#
P"2#ÐC"44#
P"2#ÐC"32#
1[159"1#
1[166"1#
1[224"1#
0[654"5#
0[721"5#
0[793"5#
0[731"5#
0[728"5#
0[706"5#
S"1#ÐCo"0#ÐP"1#
P"1#ÐCo"0#ÐP"0#
P"1#ÐCo"0#ÐS"0#
S"1#ÐCo"0#ÐP"2#
P"0#ÐCo"0#ÐP"2#
S"1#ÐCo"0#ÐS"2#
P"0#ÐCo"0#ÐS"2#
P"2#ÐCo"0#ÐS"2#
77[26"5#
84[57"5#
82[99"5#
80[24"5#
056[56"6#
72[32"5#
75[47"5#
70[61"5#
S"1#ÐCo"0#ÐP"0#
S"1#ÐCo"0#ÐS"0#
P"0#ÐCo"0#ÐS"0#
P"1#ÐCo"0#ÐP"2#
S"0#ÐCo"0#ÐP"2#
P"1#ÐCo"0#ÐS"2#
S"0#ÐCo"0#ÐS"2#
80[06"5#
066[28"5#
75[38"5#
85[34"5#
89[69"5#
060[43"6#
84[16"5#

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P[ Perez!Lourido et al[
ꢀ
Fig[ 1[ The molecular structure of ðNi"1!"Ph1P#!5!"Me2Si#C5H2S#1Ł[
in the mentioned complex[ These structural con! Structure of ðCo"1!"Ph1PO#!5!"Me2S#C5H2S#1Ł\ 4
siderations reveal that the introduction of a tri!
alkylsilyl group to the ligand has a negligible in~uence
on the structural parameters of the compound[
The crystal structure of 4 shows the presence of two
independent but structurally similar\ molecules in the
Ä
Table 2[ Selected bond lengths "A# and angles "># for ðNi"1!"Ph1P#!5!
"Me2Si#C5H2S#1Ł[ 3
NiÐS
1[040"2#
1[061"2#
0[669"00#
0[798"09#
NiÐS$0
NiÐP
PÐC"0#
1[040"2#
1[061"2#
0[681"00#
0[721"00#
89[85"01#
78[93"01#
079[9
NiÐP$0
SÐC"1#
PÐC"6#
PÐC"02#
SÐNiÐP$0
SÐNiÐP
SÐNiÐS$0
S$0ÐNiÐP$0
S$0ÐNiÐP
C"1#ÐSÐNi
C"1#ÐC"0#ÐP
C"0#ÐC"1#ÐS
079[9
78[93"01#
89[8"01#
098[1"3#
005[8"8#
006[9"8#
P$0ÐNiÐP
C"0#ÐPÐNi
C"1#ÐSÐNi
096[7"3#
098[1"3#
Symmetry transformations used to generate equivalent atoms] $0−x¦0\
−y¦0\ −z¦0[

Synthesis and characterisation of cobalt and nickel compounds with phosphinothiol ligands
3352
asymmetric unit[ The structure of one\ with the atom parable to those found for the tetrahedral anion
labelling is given in Fig[ 2[ Selected bond distances ðCo"SC5H4#3Ł1−\ average value 1[217 A ð13\ 14Ł\ or in
Ä
−
Ä
and angles with the estimated standard deviations are ðCo"SC09H02#2CH2CNŁ \ average value 1[17 A ð15Ł[
Ä
given in Table 3[ The compound consists of discrete Similarly\ the CoÐO bond distances\ average 0[863 A\
molecules\ with the cobalt atom tetracoordinated to are in the range for those found in tetrahedral com!
two thiolate sulfur atoms and two oxygen atoms of plexes containing triphenylphos_neoxide as ligand\
Ä
two ligands\ such that the environment around the for
instance
0[860 A
"average
value#
in
Ä
central atom can be described as ðCoO1S1Ł distorted ðCoCl1"OPMe2#1Ł ð16Ł and 0[817 A "average value# in
tetrahedral\ with bond angles\ 88[35"8# and ðCoCl1"OP"CH1Ph#2#1Ł ð17Ł[
87[79"09#>\ signi_cantly distorted with respect to the
tetrahedral value[
Bond distances and angles in the coordinated ligand
are similar to those found for the free ligand ð18Ł[
The average values for the CoÐS bond lengths for Thus the average value for the PÐO bond distance in
Ä
Ä
both molecules\ 1[1727"03# A\ are normal and similar the complex\ 0[407"2# A\ is slightly higher than the
Ä
to that in Co"II# complexes with the same geometry 0[382"2# A value found in the free ligand[ This length!
and coordination number[ Thus\ these values are com! ening can be attributed to the weakening of the P1O
bond\ by coordination to the metal[
Spectroscopic studies
The IR spectra of the ligands exhibit a band in
the 1399Ð1449 cm−0 range attributed to n"SÐH#[ This
band is absent in the spectra of the complexes\ indi!
cating that the ligand is in the anionic thiolate form
in all complexes[ The complexes also show bands in
the 0499Ð0479 cm−0 region\ characteristic of aromatic
ring vibrations\ as well as bands in the 0099Ð
0999 cm−0 region attributable to n"PÐC#[ The tri!
methylsilyl derivatives show in addition a very strong
band around 739Ð749 cm−0 assignable to the n"SiÐC#
mode[ Compounds 4\ 5 and 6 show a very strong band
at 0029 cm−0 characteristic of n"PÐO#[
The FAB mass spectra of all compounds show the
molecular ion with appropriate isotope distributions[
In many cases\ ions formed by loss of one ligand from
the initial complex are also observed\ as well as a peak
attributed to the free ligand[
The magnetic moments of the Co"III# complexes
show that these complexes are diamagnetic\ as
Fig[ 2[ The molecular structure of ðCo"1!"Ph1PO#!5!"Me2Si#
C5H2S#1Ł[
Ä
Table 3[ Selected bond lengths "A# and angles "># for ðCo"1!"Ph1PO#!5!
"Me2Si#C5H2S#1Ł[ 4
Co"0#ÐO"0#
Co"1#ÐO"2#
Co"0#ÐS"0#
Co"1#ÐS"2#
S"0#ÐC"10#
S"2#ÐC"50#
P"0#ÐO"0#
P"2#ÐO"2#
0[867"3#
0[864"2#
1[1715"03#
1[1650"03#
0[661"4#
0[664"3#
0[405"2#
0[410"2#
Co"0#ÐO"1#
0[850"2#
0[872"2#
1[1619"03#
1[2934"03#
0[657"3#
0[660"4#
0[419"2#
0[406"2#
Co"1#ÐO"3#
Co"0#ÐS"1#
Co"1#ÐS"3#
S"1#ÐC"40#
S"3#ÐC"000#
P"1#ÐO"1#
P"3#ÐO"3#
O"1#ÐCo"0#ÐO"0#
O"0#ÐCo"0#ÐS"1#
O"0#ÐCo"0#ÐS"0#
O"2#ÐCo"1#ÐO"3#
O"3#ÐCo"1#ÐS"2#
O"3#ÐCo"1#ÐS"3#
092[2"1#
O"1#ÐCo"0#ÐS"1#
O"1#ÐCo"0#ÐS"0#
S"1#ÐCo"0#ÐS"0#
O"2#ÐCo"1#ÐS"2#
O"2#ÐCo"1#ÐS"3#
S"2#ÐCo"1#ÐS"3#
88[63"8#
015[27"0#
88[08"09#
097[4"1#
013[07"0#
87[36"09#
013[56"0#
095[04"4#
88[02"09#
019[28"0#
096[78"4#

3353
P[ Perez!Lourido et al[
ꢀ
expected for low spin d5 octahedral complexes[ The
solid state electronic spectra of these complexes show
two bands near 05\999 and 14\999 cm−0[ The _rst band
7[ Dilworth\ J[ R[\ Zheng\ S[ and Lu\ S[\ Wu\ Q[\
Trans[ Met[ Chem[\ 0881\ 06\ 253[
8[ Dilworth\ J[ R[\ Lu\ C[\ Miller\ J[ R[ and Zheng\
Y[\ J[ Chem[ Soc[ Dalton Trans[\ 0884\ 0846[
09[ Chadha\ R[ K[\ Kumar\ R[\ Romero\ J[ and Tuck\
D[ G[\ Can[ J[ Chem[\ 0877\ 55\ 1040[
0
is due to T0g30A0g transition and the second to
0T1g30A0g transition ð29Ł[ The nickel complexes are
also diamagnetic\ compatible with the square planar
coordination around the metal[ The solid!state elec!
tronic spectra of these complexes show two bands at
ca[ 05\999Ð06\999 and 11\999Ð13\999 cm−0\ which can
00[ Castro\ R[\ Garc(a!Vazquez\ J[ A[\ Romero\ J[\
ꢀ
ꢀ
Sousa\ A[\ Pritchard\ R[ and McAulife\ C[ A[\ J[
Chem[ Soc[ Dalton Trans[\ 0883\ 0004[
01[ Castro\ J[ A[\ Romero\ J[\ Garc(a!Vazquez\ J[ A[\
ꢀ
ꢀ
0
0
be attributed to the B0g30A0g and E0g30A0g tran!
sitions\ characteristic of nickel compounds in a
square!planar environment ð29Ł[
Castineiras\ A[\ Sousa\ A[ and Zubieta\ J[\ Poly!
½
hedron\ 0884\ 03\ 1730[
02[ Talloꢀn\ J[\ Garc(a!Vazquez\ J[ A[\ Romero\ J[\
ꢀ
ꢀ
Louro\ M[ S[\ Sousa\ A[\ Chem\ Q[\ Chang\ Y[
The diamagnetic nature of these complexes "except
compound 4# allowed their study by in solution[ In no
and Zubieta\ J[\ Polyhedron\ 0884\ 03\ 1298[
03[ Perez!Lourido\ P[ A[\ Garcꢀ(a!Vazquez\ J[ A[\
ꢀ
ꢀ
0
instance do the H NMR spectra show the thiol !SH
Romero\ J[\ Louro\ M[ L[\ Sousa\ A[\ Chem\ Q[\
Chang\ Y[ and Zubieta\ J[\ J[ Chem[ Soc[ Dalton
Trans[\ 0885\ 1936[
signal of the free ligand around 3[0 ppm\ proving that
the ligand is in the monoanionic form in all complexes[
The spectra also show multiplets over 7[9Ð5[4 ppm
characteristic of the phenyl groups[ The 0H of ðCo"1!
"Ph1P#!5!"Me2Si#C5H2S#2Ł shows the presence of
three nonequivalent trimethylsilyl groups\ at 9[09\
9[29 and 9[49 ppm\ indicating that the meridional con!
formation of the ligands found in the solid state is
maintained in solution[ This is corroborated by the
presence of three signals in the 20P NMR spectra at
28\ 32 and 34 ppm corresponding to the nonequivalent
phosphorus in the meridional conformation[ By
contrast\ the 0H NMR of ðCo"1!"Ph1PO#!5!"Me2Si#
C5H2S#2Ł shows only a singlet at 9[24 ppm\ attributable
to the !SiMe2 groups\ indicating that the ligands in
this complex are equivalent and therefore that the
compound has a facial arrangement of the ligands in
solution[ The 20P NMR of this compound shows only
one signal at 30[5 ppm\ as expected for this ligand
arrangement[
04[ Block\ E[\ Ofori!Okai\ G[\ Kang\ H[ and Zubieta\
J[\ Inor`[ Chim[ Acta\ 0880\ 077\ 6[
05[ Block\ E[\ Ofori!Okai\ G[ and Zubieta\ J[\ J[ Am[
Chem[ Soc[\ 0878\ 000\ 1216[
06[ Habeeb\ J[ J[\ Tuck\ D[ G[ and Walters\ F[ H[\ J[
Coord[ Chem[\ 0867\ 7\ 16[
07[ Cromer\ D[ T[\ Waber\ J[ T[\ International Tables
for X!ray Crystallo`raphy\ Vol[ IV\ Table 1[1A[
The Kynoch Press\ Birmingham\ 0863[
08[ Cromer\ D[ T[\ International Tables for X!ray
Crystallo`raphy\ Vol[ IV\ Table 1[2[0[ The Kyn!
och Press\ Birmingham\ 0863[ [
19[ Sheldrick\ G[ M[\ SHELXTL!PLUS pro`ram
packa`e "PC Version# for the determination of
crystal structures\ Release 3[9[ Siemens Analytical
X!ray Instruments\ Madison WI\ 0889[
10[ Castro\ J[ A[\ Romero\ J[\ Garcꢀ(a!Vazquez\ L[
ꢀ
A[\ Duran\ M[ L[\ Sousa\ A[\ Castellano\ E[ E[\
ꢀ
Zukerman!Schepector\ J[\ Polyhedron\ 0881\ 00\
124[
11[ Shannon\ R[ D[\ In Structure and bondin` in crys!
tals\ Vol[ 1\ Chap[ 05\ ed[ M[ O|Kee}e and A[
Navrotsky\ Academic Press\ New York\ 0870[
12[ Kasiwabara\ K[\ Kita\ M[\ Masuda\ H[\ Kurachi\
S[ and Oliba\ S[\ Bull[ Chem[ Soc[ Jpn[\ 0884\ 57\
772[
Acknowled`ements*We thank the Xunta de Galicia
"Xuga!19205B85# for _nancial support[
13[ Coucouvanis\ D[\ Swenson\ D[\ Baenzinger\ N[
C[\ Murphy\ C[\ Holah\ D[ G[\ Sfarnas\ N[\ Sim!
opoulos\ A[ and Kostikas\ A[\ J[ Am[ Chem[ Soc[\
0870\ 092\ 2249[
14[ Hagen\ K[ S[ and Holm\ R[ H[\ Inor`[ Chem[\
0873\ 12\ 307[
REFERENCES
0[ Raper\ E[ S[\ Coord[ Chem[ Rev[\ 0885\ 042\ 088[
1[ Raper\ E[ S[\ Coord[ Chem[ Rev[\ 0886\ 054\ 364[
2[ Krebs\ B[ and Henkel\ G[\ An`ew[ Chem[ Int[ Ed[
En`l[\ 0880\ 29\ 658[
3[ Dance\ I[ G[\ Polyhedron\ 0875\ 4\ 0926[
4[ Castro\ R[\ Romero\ J[\ Garc(a!Vazquez\ J[ A[\
Sousa\ A[\ Chang\ Y[ D[ and Zubieta\ J[\ Inor`[
Chim[ Acta\ 0885\ 234\ 008[
5[ Block\ E[\ Kang\ H[\ Ofori!Okai\ G[ and Zubieta\
J[\ Inor`[ Chim[ Acta\ 0878\ 055\ 044[
15[ Koch\ S[ A[\ Fikar\ R[\ Millar\ M[ and O|Sullivan\
T[\ Inor`[ Chem[\ 0873\ 12\ 010[
16[ Menu\ M[!J[\ Simard\ M[\ Beauchamp\ A[\ KoÃnig\
H[\ Dartiguenave\ M[\ Dartiguenave\ Y[ and
Klein\ H[\ Acta Cryst[ C\ 0878\ 34\ 0586[
17[ De Almeida Santos\ R[ H[ and Mascarenhas\ Y[\
J[ Coord[ Chem[\ 0868\ 8\ 48[
ꢀ
ꢀ
18[ Perez!Lourido\ P[\ Romero\ J[\ Garc(a!Vazquez\
ꢀ
ꢀ
ꢀ
6[ Dilworth\ J[ R[\ Hutson\ A[ J[\ Morton\ S[\
Harman\ M[\ Hursthouse\ M[ B[\ Zubieta\ J[\
Archer\ C[ M[ and Kelly\ J[ D[\ Polyhedron\ 0881\
00\ 1040[
J[ A[\ Sousa\ A[\ Zubieta\ J[ and Maresca\ K[\
unpublishied results[
29[ Lever\ A[ B[ P[\ Inor`anic Electronic Spectroscopy\
1nd edn[\ Elsevier\ Amsterdam[ 0873[