Persulfurated complexes of palladium(II) and platinum(II) with fluorinated aryl-thiolates. X-ray structure of [Pt(SC6F5)2(CH3SCH(CH 3)CH(CH3)SCH3)]

Article abstract of DOI:10.1016/S0277-5387(98)00214-9

The syntheses of the persulfurated [M(SR_F)₂(CH₃SCH(CH₃)CH(CH ₃)SCH₃)], M=Pd or Pt; R_F=C₆F₅ or C₆F₄H-4 compounds allow the separation o

Full text of DOI:10.1016/S0277-5387(98)00214-9

Polyhedron Vol[ 06\ No[ 12Ð13\ pp[ 3980Ð3988\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166Ð4276"87#99103Ð8
Persulfurated complexes of palladium"II# and
platinum"II# with ~uorinated aryl!thiolates[
X!ray structure of
ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł
Erika Martin\ꢀa Beatriz Toledo\a Hugo Torrens\a Fernando J[ Lahozb
and Pilar Terrerosc
aDEPg[\ F[ Qu(mica\ UNAM\ 93409\ Mexico D[F[\ Mexico
ꢁ
bDepto[ de Qu(mica Inorganica\ ICMA!CSIC\ Universidad de Zaragoza\ 49998 Zaragoza\ Spain
ꢁ
ꢁ
cICP!CSIC\ Cantoblanco\ 17938 Madrid\ Spain
"Received 01 February 0887^ accepted 10 May 0887#
Abstract*The syntheses of the persulfurated ðM"SRF#1"CH2SCH"CH2#CH"CH2#SCH2#Ł\ MꢂPd or Pt^
RFꢂC5F4 or C5F3H!3 compounds allow the separation of two diastereomers and the NMR detection of _ve
conformers "three anti and two syn# of each compound[ 0H\ 08F and 084Pt NMR data have been used to assign
each conformer and to obtain their relative populations as well as to follow their equilibrium at high tempera!
tures[ The X!ray di}raction molecular and crystalline structure of ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł
has been determined[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] persulfurated^ crystal structure^ ~uorothiolates^ palladium^ platinum^ sulfur inversion[
———————————————————————————————————————————————
0[ INTRODUCTION
istry of metal centres surrounded exclusively by sulfur
atoms and as part of the research done\ in this paper
we report the syntheses of ðM"SRF#1"CH!
2SCH"CH2#CH"CH2#SCH2#Ł\ MꢂPd\ SRFꢂSC5F4\ 0^
SRFꢂSC5RH!3\ 1^ MꢂPt\ SRFꢂSC5F4\ 2^
SRFꢂSC5F3H!3\ 3^ the separation of two sets of iso!
mers for each complex and the X!ray di}raction
crystal structure of a diastereomer of ðPt"SC5F4#1"CH!
2SCH"CH2#CH"CH2#SCH2#Ł[ The separation of both
diastereomers allows\ for the _rst time\ a direct identi!
_cation of the stereoisomers present in solution by
0H\ 08F and 084Pt NMR[
The chemistry of co!ordination compounds with
metal centres surrounded exclusively by sulfur donor
ligands has been extensively examined[ The interest in
this area is due to its relevance to i[a[ catalysis\ bio!
inorganics and structural chemistry ð0Ð5Ł[
For complexes containing chiral three co!ordinated
sulfur atoms\ several structural and kinetic studies
have been undertaken with regard to the inter!
conversion of isomers that arises from con_guration
inversion at the sulfur atoms ð6\7Ł[
However\ for those complexes with three or more
possible NMR!observable conformers ð8\09Ł\ since
there is no conclusive evidence to distinguish among
spectroscopic signals arising from di}erent con!
formers\ seldom is a precise assignment accomplished
ð00Ð02Ł[
1[ EXPERIMENTAL
ðMCl1""meso\ rac#!CH2SCH"CH2#CH"CH2#SCH2#Ł\
MꢂPd or Pt ð06Ł\ Pb"SC5F4#1 ð07Ł and Pb"SC5F3H!3#1
ð08Ł were prepared according to published methods[
After ðMCl1""meso\ rac#!CH2SCH"CH2#CH"CH2#
SCH2#Ł\ MꢂPd or Pt "0[1 mmol# and Pb"SC5F4#1 or
Pb"SC5F3H!3#1 "0[1 mmol# were dissolved in 59 ml of
Previously ð03Ð05Ł we were interested in the chem!
ꢀ Author to whom correspondence should be addressed[
3980

3981
Erika Martin et al[
acetone\ the resulting suspensions were magnetically in acetone proceeded as expected to give ðM"SRF#1
stirred for 1 h at room temperature[ PbCl1 was then ""meso\ rac#!CH2SCH"CH2#CH"CH2#SCH2#Ł\ MꢂPd\
_ltered o} and the clear orange or yellow solutions SRFꢂSC5F4\ 0^ SRFꢂSC5F3H!3\ 1^ MꢂPt\ SRFꢂ
were evaporated to dryness "yields] 0ꢂ89)\ 1ꢂ73)\ SC5F4\ 2^ SRFꢂSC5F3H!3\ 3^ as orangeÐred "0 and 1#
2ꢂ85) and 3ꢂ80)#[
or yellow crystalline "2 and 3#\ air stable complexes
9[64 g of silica!gel were added to the solids "ca[ which are soluble in acetone and dichloromethane[
9[04 g# after they were dissolved in ca[ 04 ml of Analytical data consistent with the given formulation
acetone[ For each compound\ the solvent was evap! have been deposited as supplementary data[
orated and the impregnated silica was placed on top
Infrared spectra show characteristic absorption
of a chromatographic column and eluted with chloro! bands of the ~uorinated moieties] 0404\ 0379\ 0974\
form]acetone "09]0# to obtain solutions of cis ðRfꢂ2[7\ 864 and 744 cm−0 for SRFꢂSC5F4 and 0379\ 0329\
0!cis "12[4)#^ Rfꢂ2[5\ 1!cis "36[8)#^ Rfꢂ2[0\ 2!cis 0054 and 809 cm−0 corresponding to SRFꢂSC5F3H!3
"30[2)#^ Rfꢂ2[9\ 3!cis "32[1)#Ł and trans ðRfꢂ3[8\ 0! ð08Ł[ Other infrared frequencies agree with the dithi!
trans "09[8)#^ Rfꢂ3[6\ 1!trans "14[32)#^ Rfꢂ3[3\ 2! olate ligand expected absorptions\ but have been omit!
trans "37[8)#^ Rfꢂ3[1\ 3!trans "40[7)#Ł isomers[
ted since they are of limited value to the following
Slow evaporation of these solutions at room tem! discussion[
perature a}orded orange powders or yellow crystals[
From each compound 0 to 3\ two isomers were
Analytical data were determined by Galbraith Lab! separated by dry column chromatography on silica!
oratories\ U[S[A[
gel by using a chloroformÐacetone mixture as eluent
Infrared spectra were recorded over the 3999Ð as described in Section 1[
199 cm−0 range as CsI pellets on a Perkin!Elmer 0229
instrument equipped with a data station[
Single crystals of the 2!cis\ were isolated by slow
evaporation of chloroform]acetone solutions at room
0H\ 08F and 084Pt NMR spectra were measured with temperature[ The X!ray di}raction structure of 2!cis
a SDS!259 MHz and a modi_ed NT!259 spectrometer is shown in Fig[ 0 and selected geometric data are
operating at 259\ 171[12 and 66[0 MHz\ respectively\ collected in Table 0[
by Spectral Data Services "IL\ U[S[A[#[ Chemical
The molecules exhibit a slightly distorted square!
shifts are relative to TMS\ dꢂ9 "0H#^ CFCl2\ dꢂ9 " planar arrangement around the platinum centre\ with
08F# and Na1ðPtCl3Ł:D1O\ dꢂ9 "084Pt#[ A standard four co!ordinated sulfur atoms showing a clear sp2
variable temperature unit was used to control the hybridisation[ The racemic mixture of the cis isomer
probe temperature\ which was checked periodically crystallise as the conformer with a formal alternate
by a thermocouple to ensure that temperature read! chiral con_guration\ RSRS or SRSR\ in the chiral
ings were kept within 20>C[ Palladium complexes atoms of the chelated thioether ligand CH2S!
were studied in "CD2#1CO from −26 to 39>C and CH"CH2#CH"CH2#SCH2[ The molecular structure of
platinum complexes were studied in "CD2#1CO at 2!cis corresponds to isomer A "see Fig[ 3 below#[
room temperature and in "CD2#1SO at high tem!
peratures[
Sharp et al[ ð10Ł have found a closely related
structure for ðPtCl1"CH2SCH"CF2#CH"CF2#SCH2#Ł in
Crystallographic data for ðPt"SC5F4#1"CH! which the tri~uomethyl groups lie on the opposite side
2SCH"CH2#CH"CH2#SCH2#Ł 2!cis] C07H03F09PtS3\ of the chelate ring from the methyl substituents[
Mꢂ632[50\
aꢂ6[091"0#\
bꢂ83[60"1#>\
bꢂ08[955"2#\
The observed mean values for the PtÐS "PtÐSRF
2
1
Ä
Ä
Ä
cꢂ05[688"2# A\
Uꢂ1156[9"5# A \ 1[206 and PtÐSC1 1[180 A# and SÐC ðSÐC"sp # 0[654
Tꢂ184 K\ space group P10:n\ Zꢂ3\ rꢂ1[068 g cm−2
\
and SÐC"sp # 0[706 AŁ bond distances are similar to
2
Ä
mꢂ55[82 cm−0
[
A
crystal
of
dimensions those found on the related trans!ðPt"SC5F4#"SEt1#1Ł
9[06×9[01×9[07 mm was used for indexing and ð05Ł ðPtÐSRF 1[212\ PtÐSC1 1[291^ SÐC"sp1# 0[659\ SÐ
2
Ä
intensity data collection in the scan mode by using C"sp # 0[797 AŁ[
graphite monochromatized Mo!Ka radiation in a Sie!
For ðPtCl1"CH2SCH"CF2#CH"CF2#SCH2#Ł ð10Ł the
mens AED di}ractometer using v:1u scans platinumÐsulfur mean distance is slightly shorter "PtÐ
Ä
"2²1u²49>#[ They were corrected for Lorentz\ polar! SC1 1[126 A# probably re~ecting a lower trans!in~u!
isation and absorption e}ects[ The structure was ence of the chloride ligand as compared with that
solved by the Patterson method[ All non!hydrogen of the SC5F−4 moiety ð11Ł[ In general\ sulfurÐcarbon
atoms were anisotropically re_ned "SHELX!65# ð19Ł lengths agree satisfactorily with the ranges described
and hydrogen atoms were included in the observed for this type of bond distance ð12Ł[
positions[ Final R and Rw values were 9[913 for 2060
observed re~ections ðFr4s"F#Ł[
The isomers separated from these complexes can be
explained simply in terms of the relative orientation
of the substituents on methine groups "cis and trans
diastereomers#[ As shown in Fig[ 1\ the ring is puck!
ered at the carbon atoms but\ as is the case with _ve
membered rings at room temperature\ there is fast
2[ RESULTS AND DISCUSSION
Methathetical reactions of ðMCl1""meso\ rac#! ring inversion in all species investigated to date[ At
CH2SCH"CH2#CH"CH2#SCH2#Ł\ MꢂPd or Pt with low temperature\ however\ few conformers have been
the anionic pseudohalogens "SC5F4#− or "SC5F3H!3#− previously identi_ed in solution ð06Ł[

Persulfurated complexes of palladium"II# and platinum"II# with ~uorinated aryl!thiolates
3982
Fig[ 0[ X!ray structure of ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł\ 2!cis[
Ä
Table 0[ Selected molecular dimensions "bond lengths in A\ angles in ># for
ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł 2!cis with e[s[d[s[ in parentheses
PtÐS"0#
PtÐS"2#
S"0#ÐC"0#
S"1#ÐC"3#
S"2#ÐC"6#
1[182"0#
1[212"0#
0[795"4#
0[716"5#
0[650"4#
PtÐS"1#
PtÐS"3#
S"0#ÐC"1#
S"1#ÐC"5#
S"3#ÐC"02#
1[178"0#
1[209"0#
0[728"4#
0[686"5#
0[657"4#
S"2#ÐPtÐS"3#
S"1#ÐPtÐS"2#
S"0#ÐPtÐS"2#
PtÐS"0#ÐC"1#
PtÐS"1#ÐC"5#
PtÐS"2#ÐC"6#
78[84"4#
73[70"4#
060[45"4#
091[52"1#
093[70"1#
097[72"1#
S"1#ÐPtÐS"3#
S"0#ÐPtÐS"3#
S"0#ÐPtÐS"1#
PtÐS"0#ÐC"0#
PtÐS"1#ÐC"3#
PtÐS"3#ÐC"O#
062[65"4#
85[82"4#
77[48"4#
009[69"1#
092[24"1#
009[86"1#
Fig[ 1[ Diagram representing compounds ðM"SRF#1"CH2SCH"CH2#CH"CH2#SCH2#Ł[ The M"SRF#1 unit lies perpendicular
to the paper and in the plane de_ned by the sulfur atoms[

3983
Erika Martin et al[
NMR spectra of compounds cis and trans revealed 2[0[ Cis!diastereomers
the expected presence of further isomeric forms arising
from the relative position of the methyl substituents
on the sulfur atoms with respect to the plane of the
metal co!ordination\ giving rise to anti and syn
isomers\ as exempli_ed in Fig[ 2[
Anti and syn conformers can undergo an inter!
conversion process through inversion of con_guration
at the sulfur centers[ These conformational changes
of the sulfur substituents are slow enough as to be
detected by NMR experiments[
All together\ the relative orientations of both sulfur
and carbon substituents can\ therefore\ generate two
di}erent sets of non!interconvertable isomers "cis and
trans# with three NMR!detectable and inter!
convertable conformers in each set\ as shown on Fig[
3[
Therefore\ in terms of NMR spectroscopy\ both
methyl substituents on the sulfur atoms "CH2ÐS# are
equivalent in isomers A\ C\ D and F\ whereas isomers
B and E bear pairs of magnetically non!equivalent
CH2ÐS moieties[ Exactly the same is valid when the
CH2ÐC and RFÐS fragments are considered[
NMR selected parameters for compounds 0!cis to
3!cis are collected in Table 1[
0H NMR spectra of isomers cis show three doublets
arising from the CH2ÐC fragments[ In all cases two of
these doublets have exactly the same intensity\ which
suggests that they arise from two non!equivalent
methyls attached to the same molecule[ These absorp!
tions can\ therefore\ be assigned unambiguously to
isomer B in Fig[ 3[ The third doublet arises from an
isomer with magnetically equivalent methyl substitu!
ents\ which is the case of either A or C^ no de_nite
assignment can be made at this point\ however[
Proton NMR spectra also show a complicated over!
lap of signals due to the !CHÐCH! skeleton and\ as
before\ three signals for the CH2ÐS substituents which\
for compounds 2 and 3\ exhibit satellites characteristic
of magnetic coupling with platinum "084Pt\ 23) abun!
dance#[ JPtÐH"2!cis#ꢂ31[0 Hz and JPtÐH"3!cis#ꢂ
31[0 Hz[
In addition\ when RFꢂC5F3H!3 "cis!compounds 1
and 3#\ three triplets of triplets\ characteristic of the
X part of two distinct A1B1X magnetic systems\ are
detected[
This fact is of interest and seldom observed since
practically all spectroscopic studies on this type of
compound focus on the neutral ligand[ Very few of
the anionic ligands used before are suitable for NMR
observation[ The ~uorothiolates involved in this work
thus allow the distinction between magnetic non!
equivalence brought up by the molecular asymmetry[
The presence of distinguishable thiolates is also
re~ected on the 08F NMR spectra\ showing three
doublets for the ortho!~uorine atoms\ a complicated
multiplet of overlapping signals due to meta!~uorine
Fig[ 2[ Anti and syn isomers of ðM"SRF#1"CH2SCH
"CH2#CH"CH2#SCH2#Ł[
Fig[ 3[ Cis and trans isomers of ðM"SRF#1"CH2SCH"CH2#CH"CH2#SCH2#Ł[

Persulfurated complexes of palladium"II# and platinum"II# with ~uorinated aryl!thiolates
3984
Table 1[ NMR selected parameters for cis!diastereomers of ðM"SRF#1"CH2SCH"CH2#CH"CH2#SCH2#Ł 0Ð3\ MꢂPd\
"CD2#1CO at 126 K^ MꢂPt\ "CD2#1CO at 187 K
d|s
J|s
Pt
Hp
Fo
Fp
2JFo−Fm
2JFm−Fp"H# 3JFo−Fp"H#
0
A
−020[84d
−051[92t
16[8
19[3
09[1
10[2
09[2
−
6[4
6[8
6[1
B
−021[29d
−021[52d
−051[52t
−051[54t
1
A
6[29tt
−021[62m
−
17[9
−
B
6[17tt
6[20tt
−022[95m
−022[16m
2
A
−3142s
−3140s
−029[80dd
−050[23tt
B
−020[05dd
−020[31dd
−050[53t
−050[65t
3
A
−3239s
−3228s
6[96tt
−021[51m
B
6[95tt
6[97tt
−021[77m
−022[66m
atoms and\ for complexes 0 and 2\ three triplets arising
According to that assignment\ the relative popu!
from the ~uorine atoms in the para position of the lation of isomers A and B "Fig[ 3#\ for compounds 0
~uorinated ring ðFig[ 4"a#Ł[
to 3\ are given in Table 2[
This spectroscopic information is consistent with
the presence of only two out of the three\ A\ B and C
possible isomers[ Considering the multiplicity 2[1[ Trans!diastereomers
observed on the NMR signals\ isomer B can be recog!
nised unambiguously\ but a distinction between A and
C "Fig[ 3# is not evident[
Further evidence for the presence of a single pair of
NMR selected parameters for compounds 0!trans
to 3!trans are collected in Table 3[
0H NMR spectra of complexes trans show a
isomers was able to be gained from 084PtÐ"0H# NMR complex\ ill!de_ned multiplet on the CH2ÐC region[
spectra of compounds 2!cis and 3!cis at room tem! Four signals\ however\ arising from the CH2ÐS frag!
perature[ 2!cis shows two singlets at dPtꢂ−3142 and ments\ were clearly observed[
−3140 ppm with a relative proportion of 4[8 to 0[ 3!
cis shows two absorptions at dPtꢂ−3239 and ellites characteristic of 0HÐ084Pt magnetic coupling
−3228 ppm with 2[4 to 0 relative intensities[ with platinum
084Pt\ 23) abundance#[ JPtÐH"2!
Molecular models indicate extensive steric inter! trans#ꢂ30[3 Hz and JPtÐH"3!trans#ꢂ31[4 Hz[
actions between the sulfur and carbon substituents For all compounds 0 to 3\ two of these signals have
For compounds 2 and 3\ these signals exhibit sat!
"
and they appear to be in the order A³B³C[ In agree! exactly the same intensity\ suggesting that they arise
ment with this order in which the least hindered iso! from two non!equivalent methyls attached to the same
mers are predicted to have equivalent methylÐsulfur molecule[ These absorptions can\ therefore\ be
substituents\ it is reasonable to assume that the most assigned unambiguously to isomer E in Fig[ 3[ The
abundant isomer is A\ while C has the lowest\ unob! remaining two signals are resonances from isomers D
servable\ concentration[ Assignment of signals at and F\ both having magnetically equivalent methyl
dPtꢂ−3142 "2!cis# and −3239 "3!cis# ppm to isomers substituents[
A rather than to isomers C\ seems further supported
Proton NMR spectra also display a complex multi!
by the fact that the structure found in the solid state plet of overlapping signals due to the !CHÐCH!
for ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł is in skeleton[ In addition\ when RFꢂC5F3H!3 "trans!com!
fact that of isomer A[
pounds 1 and 3#\ four signals characteristic of the X

3985
Erika Martin et al[
Fig[ 4[ 08F NMR of para!~uorine region of ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł 2!cis "a# and 2!trans "b#[
Table 2[ Relative isomeric populations for ðM"SRF#1"CH2
SCH"CH2#CH"CH2#SCH2#Ł\ MꢂPd "126 K#\ RFꢂC5F4 0^
C5F3H!3 1^ MꢂPt"187 K#\ RFꢂC5F4 2^ C5F3H!3 3
2!trans and 3!trans which show\ at room temperature\
three singlets at dPtꢂ−3141\ −3146 and −3150 ppm
and dPtꢂ−3228\ −3231 and −3232 ppm\ respec!
tively[ The relative intensities of these signals are
0[2]0[0]0 for 2!trans and 0[1]0[0]0 for 3!trans[
Cis
Trans
As seen before\ molecular models indicate con!
siderable steric interactions between the sulfur and
carbon substituents\ which appear to be in the order
D³E³F[ In agreement with this order in which the
least hindered isomers are predicted to have anti and
equivalent sulfur substituents\ the most abundant iso!
mer is probably D\ whereas F appears to be the least
abundant[
A
B
C
D
E
F
0
1
2
3
5[2
4[5
4[8
2[4
0
0
0
0
−
−
−
−
0[0
0[0
0[2
0[1
0[3
0[2
0[0
0[0
0
0
0
0
The relative populations assigned to trans!isomers
D\ E and F "Fig[ 3#\ for compounds 0 to 3\ are given
in Table 2[
Conformers A and B\ on the one hand\ as well as
D\ E and F\ on the other\ are involved in dynamic
equilibria due to a con_guration inversion at the thi!
oether sulfur atoms[ The pyramidal inversion is a rela!
tively slow process suitable for detection within the
NMR time scale as the individual absorptions from
each isomer coalesce into a single averaged resonance[
As expected\ the thiolate ligands seem to have fast
free rotation and\ at room temperature and higher\ do
not participate in the ~uxionality of these molecules[
For comparable compounds\ palladium derivatives
show lower coalescence temperatures than does plati!
part of three di}erent A1B1X magnetic systems\ are
detected[
08F NMR spectra show four doublets for the ortho!
~uorine atoms\ a complicated multiplet of overlapping
signals due to meta!~uorine atoms and\ for complexes
0 and 2\ four triplets of triplets arising from the ~u!
orine atoms in the para position of the ~uorinated
ring ðFig[ 4"b#Ł[ No 08FÐ084Pt magnetic couplings were
observed[
The available spectroscopic information is con!
sistent with the presence of isomers D\ E and F "Fig[
3# in solution of compounds 0!trans to 3!trans[
Further evidence of such an isomeric distribution is num[ This can be attributed to the more e}ective
gained from 084PtÐ"0H# NMR spectra of compounds 2p"S#Ð3d"Pd# overlap compared with the 2p"S#Ð4d"Pt#

Persulfurated complexes of palladium"II# and platinum"II# with ~uorinated aryl!thiolates
3986
Table 3[ NMR selected parameters for trans!diastereomers of ðM"SRF#1"CH2SCH"CH2#CH"CH2#SCH2#Ł 0Ð3\ MꢂPd\
"CD2#1CO at 126 K^ MꢂPt\ "CD2#1CO at 187 K
d|s
J|s
Pt
Hp
Fo
Fp
2JFo−Fm
2JFm−Fp"H# 3JFo−Fp"H#
0
D
E
−020[76d
−020[67d
−020[84d
−021[34d
−051[08t
−050[64t
−051[18t
−051[80t
16[0
10[9
09[1
11[5
09[2
−
6[4
7[4
6[1
F
1
D
6[29tt
−021[69m
−022[98m
E
F
6[18tt
6[17tt
−
17[1
−
6[15tt
2
D
E
−3141s
−3146s
−029[77dd
−029[79dd
−029[81dd
−020[33dd
−050[15tt
−050[94tt
−050[44tt
−050[87tt
F
−3150s
3
D
−3228s
−3231s
−3232s
6[97tt
−021[86m
−021[46m
E
F
6[95tt
6[96tt
6[93tt
overlap\ which allows an easier access to the transition A\B[ On the other hand\ trans!compounds 0 to 3 give
state in the case of palladium complexes ð13Ł[ In fact\ rise to two consecutive temperatures of coalescence\
palladium derivatives show slow sulfur inversion at in agreement with a process involving three species]
126 K while platinum derivatives show it at 187 K in D\E\F for which two di}erent energies of inversion
"CD2#1CO solutions[
are reasonably to be expected "Fig[ 5#[
For palladium complexes we have measured coales!
In summary\ NMR studies of each diastereomer of
cence temperatures by observing the 08F NMR spectra complexes 0 to 3 show the presence of three con!
of the thiolate moieties[ For platinum complexes\ formers of the trans isomers but only two of the cis
coalescence temperatures were determined directly isomer[ In general\ NMR spectra are quite similar and
from the variable temperature 084Pt NMR spectra[ only slight changes in the relative isomeric popu!
Coalescence temperatures are collected in Table 4[
lations were observed[ As expected\ relative abun!
Cis!compounds 0 to 3 show a single coalescence dances can be detected regardless of the observed
of signals in agreement with the fast interconversion nuclei[
Table 4[ Coalescence temperatures of the compounds 0 to 3
Compounda
Isomer
CT0b
Isomer
CT0b
CT1b
0 ðPd"SC5F4#1LŁ
1 ðPd"SC5F3H!3#1LŁ
2 ðPt"SC5F4#1LŁ
cis
cis
cis
cis
172
172
222
222
trans
trans
trans
trans
172
172
232
232
297
297
252
272
3 ðPt"SC5F3H!3#1LŁ
aLꢂCH2SCH"CH2#CH"CH2#SCH2[
bCoalescence temperature "CT# in K[

3987
Erika Martin et al[
Fig[ 5[ Variable temperature 084Pt NMR spectra of ðPt"SC5F4#1"CH2SCH"CH2#CH"CH2#SCH2#Ł 2!cis "a# and 2!trans "b#[
5[ Black\ J[ R[ and Levason\ W[\ J[ Chem[ Soc[ Dal!
ton Trans[\ 0883\ 2114[
3[ SUPPLEMENTARY MATERIAL
AVAILABLE
6[ Abel\ E[ W[\ Bhargava\ S[ K[ and Orrell\ K[ G[\
Pro`[ Inor`[ Chem[\ 0873\ 21\ 0[
Tables of analytical data are shown in Appendix A[
Crystal and intensity measurement data\ positional
parameters of calculated hydrogen atoms\ anisotropic
thermal parameters and bond distances and angles
have been deposited at Cambridge Crystallographic
Data Centre\ deposition code] 090489[
7[ Orrell\ K[ G[\ Coord[ Chem[ Rev[\ 0878\ 85\ 0[
³
8[ Orrell\ K[ G[\ Sik\ V[\ Brubaker\ C[ and McCul!
loch\ B[\ J[ Or`anomet[ Chem[\ 0873\ 165\ 156[
09[ Abel\ E[ W[\ Khan\ R[\ Kite\ K[\ Orrell\ K[ G[
³
and Sik\ V[\ J[ Chem[ Soc[ Dalton Trans[\ 0879\
0064[
00[ Abel\ E[ W[\ Coston\ T[ P[\ Higgins\ K[ M[\ Orrell\
Acknowled`ements*We wish to thank DGAPA!UNAM\
PADEP!UNAM and CONACYT for _nancial support and
to Dr Sylvain BerneÁs for his helpful assistance[
³
K[ G[\ Sik\ V[ and Cameron\ T[ S[\ J[ Chem[ Soc[
Dalton Trans[\ 0878\ 690[
01[ Abel\ E[ W[\ Moss\ I[\ Orrell\ K[ G[\ Sik\ V[\
³
Stephenson\ D[\ Bates\ P[ A[ and Hursthouse\ M[
B[\ J[ Chem[ Soc[ Dalton Trans[\ 0877\ 410[
02[ Mao\ X[!A[\ Yao\ J[!Z[\ Tian\ B[!S[ and Chen\ Y[!
Y[\ Ma`n[ Reson[ Chem[\ 0885\ 23\ 098[
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APPENDIX A
SUPPLEMENTARY ANALYTICAL DATA
The analytical data of 0Ð3 meso:rac!complexes are given in Table 5[ The analytical data of cis and trans
complexes are given in Table 6[
Table 5[ Analytical data of 0Ð3 meso:rac!complexes
Compounda
Analyses ")#b
H
C
S
0 ðPd"SC5F4#1LŁ
1 ðPd"SC5F3H!3#1LŁ
2 ðPt"SC5F4#1LŁ
21[5 "22[9#
23[3 "23[8#
17[8 "18[0#
29[0 "29[5#
1[2 "1[1#
1[7 "1[5#
0[6 "0[8#
1[3 "1[2#
08[1 "08[5#
19[3 "19[6#
06[2 "06[2#
06[8 "07[0#
3 ðPt"SC5F3H!3#1LŁ
aLꢂCH2SCH"CH2#CH"CH2#SCH2[
bCalculated values in parentheses[
Table 6[ Analytical data of cis and trans complexes
Compounda
Analyses ")#b
C
H
S
0!cis ðPd"SC5F4#1LŁ
21[7 "22[9#
21[8 "22[9#
23[6 "23[8#
23[7 "23[8#
17[8 "18[0#
18[9 "18[0#
29[3 "29[5#
29[4 "29[5#
1[2 "1[1#
1[1 "1[1#
1[5 "1[5#
1[4 "1[5#
0[7 "0[8#
1[9 "0[8#
1[3 "1[2#
1[2 "1[2#
08[4 "08[5#
08[3 "08[5#
19[4 "19[6#
19[7 "19[6#
06[2 "06[2#
06[3 "06[2#
06[8 "07[0#
07[1 "07[0#
0!trans ðPd"SC5F4#1LŁ
1!cis ðPd"SC5F3H!3#1LŁ
1!trans ðPd"SC5F3H!3#1LŁ
2!cis ðPt"SC5F4#1LŁ
2!trans ðPt"SC5F4#1LŁ
3!cis ðPt"SC5F3H!3#1LŁ
3!trans ðPt"SC5F3H!3#1LŁ
aLꢂCH2SCH"CH2#CH"CH2#SCH2[
bCalculated values in parentheses[