Diethoxy-diphenyl-dithioimidodiphosphinate

Article abstract of DOI:10.1016/S0277-5387(98)00155-7

Reaction of (EtO)₂P(S)NH₂ with Ph₂P(S)Cl in the presence of NaH gives (EtO)₂P(S)NHP(S)Ph₂ (1) which has been complexed with Zn, Pd and Pt in Zn [(EtO)₂P(S)NP(S)Ph₂]₂ 2 Pd[(EtO)₂P(S)NP(S)Ph₂]₂ 3 Pt[(EtO)₂P(S)NP(S)Ph₂]₂ 4 and [Pt(PMe₃)₂{(EtO)₂ P(S)NP(S)Ph₂}] ⁺ BPh₄^- 5. ³¹P NMR studies suggest that 3 and 4 are formed as cis/trans mixtures. The X-ray structure of 1 reveals it to be a H-bonded dimer in the solid state, whilst the structures of 3-5 contain MS₂P₂N rings in varying non-planar (chair, boat) geometries.

Full text of DOI:10.1016/S0277-5387(98)00155-7

\
Polyhedron 07 "0888# 200Ð208
PERGAMON
Diethoxy!diphenyl!dithioimidodiphosphinate
Domineco C[ Cupertinoa\ Robin W[ Keyteb\ Alexandra M[Z[ Slawinb\
J[ Derek Woollinsb\ ꢀ
a Zeneca Specialties Division\ Blackley\ Manchester M8 7ZS\ UK
b Department of Chemistry[ Loughborough University\ Loughborough\ LE00 2TU\ UK
Received 05 February 0887^ accepted 2 April 0887
Abstract
Reaction of "EtO#1P"S#NH1 with Ph1P"S#Cl in the presence of NaH gives "EtO#1P"S#NHP"S#Ph1 "0# which has been complexed
with Zn\ Pd and Pt in Zn ð"EtO#1P"S#NP"S#Ph1Ł1 1 Pdð"EtO#1P"S#NP"S#Ph1Ł1 2 Ptð"EtO#1P"S#NP"S#Ph1Ł1 3 and ðPt"PMe2#1""EtO#1
P"S#NP"S#Ph1#Ł¦BPh3− 4[ 20P NMR studies suggest that 2 and 3 are formed as cis:trans mixtures[ The X!ray structure of 0 reveals it
to be a H!bonded dimer in the solid state\ whilst the structures of 2Ð4 contain MS1P1N rings in varying non!planar "chair\ boat#
geometries[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
Keywords] Diethoxy!diphenyl!dithioimidodiphosphinate^ Coordination chemistry^ Ring conformations
0[ Introduction
been characterised spectroscopically and in four cases by
single crystal X!ray studies[
There is considerable interest in the coordination
chemistry of Ph1P"S#NHP"S#Ph1 ð0Ð8Ł[ We and others
have noted interesting behaviour in the ring con!
formations of MS1P1N species[ Notably less work has
been reported on the chemistry of the alkyl analogues
R1P"S#NHP"S#R1 with the exception of some studies on
Me1P"S#NHP"S#Me1 ð09Ł and Pr1P"S#NHP"S#Pr1 ð00Ł[
Some work on unsymmetrical species such as
Ph1P"O#NHP"Se#Ph1 has been described ð01Ł and recently
there was a report on the synthesis of Me1P"S#NHP"S#Ph1
and its cobalt complex ð02Ł[ We have also studied imido!
diphosphinates but with varying electronic rather than
steric e}ects\ and this latter paper prompts us to report
on the synthesis and some coordination chemistry of
mixed ethoxy:phenyl substituted dithiomidophos!
phinate[ Here we report the synthesis of
"EtO#1P"S#NHP"S#Ph1 "0# together with four examples of
its| coordination complexes[ The new compounds have
1[ Experimental
1[0 General
Unless stated otherwise\ all reactions were performed
under an atmosphere of oxygen!free nitrogen using stan!
dard Schlenk procedures[ All glassware was oven dried
at 099>C or ~ame dried under vacuum before use[
All solvents and reagents were purchased from
Aldrich\ BDH or Fisons and used as received[ In addition
toluene\ thf\ Et1O and petroleum ether "59Ð79# were distilled
from sodium!benzophenone under nitrogen\ and CH1Cl1
from CaH1[ CDCl2 "88¦ atom ) D# was as supplied[
20P "25[1\ 090[14\ 050[86 MHz# were recorded on JEOL
FX89Q\ Bruker AC149 or Bruker DPX399 spec!
trometers[ Chemical shifts are reported relative to 74)
H2PO3[ Infra!red spectra were recorded as KBr discs and
dichloromethane solutions in Csl cells on a PE System
1999 spectrometer[ Raman spectra were recorded on a
PE System 1999 with a diode pumped Nd:YAG laser[
Microanalyses were carried out by the respective micro!
ꢀ Corresponding author[
9166!4276:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[
PII] S9166!4276"87#99044!6

201
D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
analytical services of Loughborough University and
Zeneca Specialties Research Centre[ FAB ¦ve mass spec!
tra were recorded by the EPSRC mass spectrometry ser!
vice at Swansea and the mass spectrometry service at the
Zeneca Specialties Research Centre[
The mixture was then _ltered and the _ltrate evaporated
to dryness yielding a colourless oil[ Microanalysis cal!
culated for C21H39O3P3S3Zn] C 35[0^ H 3[7^ N 2[3)[
Observed] C 38[2^ H 5[0^ N 2[0)[ FTIR "KBr disc#] n
"PNP# 0128\ 653^ n "PS# 441\ 430^ d "NPS# 305 cm−0[ FAB
¦ve MS] m:z 722 corresponds to "Znð"EtO#1
P"S#NP"S#Ph1Ł1#¦[
1[1[ Syntheses
Ph1P"S#Cl was formed by re~uxing diphenyl!
chlorophosphine "01[29 g\ 09[9 ml\ 9[942 mol# with sulfur
"0[69 g\ 9[942 mol# overnight in toluene "29 ml# under N1[
The solvent was evaporated o} to give a clear oil "02[20 g^
20P! "0H# NMR "CDCl2#] d 68[3 ppm#[
Ph1P"S#NH1 was formed by bubbling ammonia gas
through a solution of Ph1P"S#Cl "3[99 g\ 04[73 mmol# in
ether "099 ml# for 19 minutes[ After _ltering the reaction
mixture through celite\ the _ltrate was evaporated to
dryness giving a white solid "2[51 g^ 20P!"0H# NMR
"CDCl2#] d 48[6 ppm#[
1[1[2[ Pdð"EtO#1P"S#NP"S#Ph1Ł1 2
Pd"cod#Cl1 "9[949 g\ 9[064 mmol# was added to a solu!
tion of 0 "9[024 g\ 9[240 mmol# and KOtBu "9[928 g\
9[237 mmol# in thf "19 ml# and re~uxed for 0 hour[ The
reaction changed colour from yellow to red:orange[ On
cooling the mixture was evaporated to dryness and
dichloromethane added[ The mixture was _ltered and the
_ltrate evaporated to dryness[ Crystals of 26 were grown
from dichloromethane and hexane "9[034 g\ 9[055 mml\
83[6) yield#[ Microanalysis calculated for C21H39N1
O3P3S3Pd] C 32[8^ H 3[5^ N 2[1)[ Observed] C 32[5^ H
3[5^ N 1[7)[ FTIR "KBr disc#] n "PNP# 0195\ 662^ n "PS#
"EtO#1P"S#NH1 was formed by bubbling ammonia gas
through
a solution of diethylchlorothiophosphate
452\ 444^ n "NPS# 319 cm−0
[
"13[99 g\ 19[9 ml\ 9[016 mol# in ether "099 ml# for 19
minutes[ After _ltering the reaction mixture through
celite\ the _ltrate was evaporated to dryness to give a
clear oil "10[25 g^ 20P!"0H# NMR "CDCl2#] d 63[1 ppm#[
1[1[3[ Ptð"EtO#1P"S#NP"S#Ph1Ł1 3
Pt"cod#Cl1 "9[949 g\ 9[023 mmol# was added to a solu!
tion of 0 "9[092 g\ 9[156 mmol# and KOtBu "9[929 g\
9[156 mmol# in thf "19 ml# and re~uxed for 0 hour[ The
reaction changed colour from clear to yellow[ On cooling
the mixture was evaporated to dryness and dichlo!
romethane added[ The mixture was then _ltered and the
_ltrate evaporated to dryness[ Crystals of 3 were grown
from dichloromethane and hexane "9[007 g\ 9[012 mmol\
83[3) yield#[ Microanalysis calculated for C21H39N1
O3P3S3Pt] C 28[8^ H 3[1^ N 1[8)[ Observed] C 30[1^ H
2[8^ N 2[9)[ FTIR "KBr disc#] n "PNP# 0144\ 0192^ n
1[1[0[ "EtO#1P"S#NHP"S#Ph1 0
Under anhydrous conditions\ sodium hydride "59)
dispersion in para.n oil 0[58 g\ 9[931 mol# was slowly
added to a solution of "EtO#1P"S#NH1 "1[27 g\ 9[903 mol#
in thf "29 ml# at 9>C[ The mixture was allowed to warm
to room temperature and stirred for 29 minutes\ then
Ph1P"S#Cl "2[42 g\ 9[903 mol# was added dropwise at 9>C[
After addition was complete the mixture was warmed to
room temperature and then re~uxed overnight[ After
cooling\ methanol "4 ml# was added dropwise to destroy
any excess sodium hydride[ The volume of the thf was
then reduced by half under vacuum and 1M aqueous HCl
"49 ml# was added\ producing a cloudy white mixture
which was washed with dichloromethane "2×19 ml#[ The
dichloromethane was dried over MgSO3 then evaporated
to dryness to give a white solid 0 which was recrystallised
from dichloromethane and hexane "3[11 g\ 9[900 mol\
67[2) yield\ mp 51>C#[ Microanalysis calculated for
C05H10NO1P1S1] C 38[8^ H 4[4^ N 2[5)[ Observed] C 38[7^
H 4[3^ N 2[5)[ 20P!"0H# NMR "CDCl2#] d"P0# 52[5"d#
ðP"OEt#1Ł\ d"P1# 42[2"d# ðPPh1Ł ppm[ 1J "20PA!20PX# 11[9 Hz[
FTIR "dichloromethane solution\ Csl plates at 099 mic!
rons#] n "NÐH# 2220 cm−0^ "KBr disc#] n "NÐH# 2199\ d "NÐ
"PS# 465\ 431^ n "NPS# 315 cm−0
[
1[1[4[ ðPt"PMe2#1""EtO#1P"S#NP"S#Ph1#Ł¦ BPh3−
4
Pt"PMe2#1Cl1 "9[959 g\ 9[033 mmol# and NaBPh3
"9[938 g\ 9[032 mmol# were added to a solution of 0
"9[944 g\ 9[032 mmol# and KOtBu "9[905 g\ 9[032 mmol#
in thf "29 ml# and re~uxed for 0 hour[ On cooling the
mixture was evaporated to dryness and washed with
methanol "1×4 ml#[ A white solid was _ltered o} and
crystallised from acetone "9[003 g\ 9[098 mmol\ 64[5)
yield#[ Microanalysis calculated for C35H47P3O1S1BNPt]
C 41[5^ H 4[5^ N 0[2)[ Observed] C 41[1^ H 4[5^ N 0[0)[
FTIR "KBr disc#] n "PNP# 0156\ 0195\ 673^ n "PS# 469\
428 cm−0
[
H# 0187^ n "PNP# 865\ 657^ n "PO# 0089\ n "PS# 535\ 523 cm−0
[
1[2[ Crystallo`raphy
1[1[1[ Zn ð"EtO#1P"S#NP"S#Ph1Ł1 1
Details of crystallographic parameters are summarised
in Table 0[ Crystals were mounted on quartz _bres using
araldite[ Data were collected using CuÐKa radiation and
v scans at room temperature with a Rigaku AFC6S
di}ractometer[ Intensities were corrected for Lorentz!
A solution of 0 "9[099 g\ 9[159 mmol#\ KOtBu "9[918 g\
9[159 mmol# and ZnCl1 "9[907 g\ 9[021 mmol# in thf
"19 ml# was re~uxed for 0 hour[ On cooling the mixture
was evaporated to dryness and dichloromethane added[

D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
202
polarisation and for absorption[ All non!H atoms were
re_ned anisotropically in all cases[ The positions of the
CÐH hydrogen atoms were idealised whilst the NÐH
atoms were allowed to re_ne isotropically[ Re_nements
were by full matrix least squares based on F using teXsan
ð03Ł The weighting scheme is as previously reported ð01Ł[
0[ Similarly\ Pdð"EtO#1P"S#NP"S#Ph1Ł1 "2# and Ptð"EtO#1
P"S#NP"S#Ph1Ł1 "3# were obtained from reactions with
M"cod#Cl1 as red and yellow solids respectively[ In
addition one equivalent of 0\ KOtBu and NaBPh3 were
re~uxed with PtCl1"PMe2#1 in thf to yield Pt"PMe2#1ð"Et
O#1P"S#Ph1Ł¦ BPh−3 "4\ 65) yield#[ All of the complexes
gave reasonable elemental analyses and the FAB ¦ve
mass spectra revealed the expected parent ions[ Charac!
teristic bands were observed in the FTIR[ High frequency
shifts in the n"PNP# vibration from around 849 in the free
ligand to 0128Ð0144 cm−0 are observed upon complex!
ation\ whilst the n"PS# vibration shifts from 535 to 441Ð
465 cm−0*all of these changes re~ect the changes in bond
order within the ligand due to the delocalisation of the
negative charge[ The 20P NMR spectrum "Table 1# of 1
is of the typical AX type[ However in 2 and 3 two AX
spectra were observed\ in each case the chemical shifts
were very similar as was the coupling Table 1 and this is
most likely due to the presence of the cis and trans
isomers[ Alternatively\ the crystal structure of 3 suggests
"vide infra# that there is very little energy di}erence
between the two PtS1P1N ring conformations in the solid
state and the two spectra may be due to di}erent ring
2[ Results and discussion
The synthesis of 0 was based upon a literature prep!
aration for compounds with mixed substituent groups
ð04Ł eq[ "0#[ The amine and halide are {clipped| together
with sodium hydride in thf[ Excess NaH gave the cleanest
products and better yields[ Although the reaction may\
in principle\ be performed using Ph1"S#NH1 and "EtO#1P!
"S#Cl we found that it proceeded in better yield and more
cleanly using "EtO#1P"S#NH1[ The salt was then pro!
tonated with dilute hydrochloric acid giving the neutral
ligand as an oil which was recrystallised from the mini!
mum of dichloromethane and petroleum ether giving
colourless crystals "69Ð79) yields# pure by elemental
analyses[ Characteristic bands ð09Ł were observed
"0#
in the FTIR\ n "NH# ca 2199\ d"NH# 0187\ n "PO# 0089\
n "PNP# 865\ 657 and n "PS# 535\ 523 cm−0 though n
"NH# could not be con_dently assigned[ The 20P NMR
spectrum of 0 "CDCl2\ Table 1# is of the AX type[ The
phosphorus centre with ethoxy substituents appears
around 53 ppm as opposed to 42 ppm for the phenyl
substituted phosphorus with 1J"20P!20P# coupling of
11[9 Hz in reasonable agreement for disulfur compounds
of this type[ Solid state 20P NMR for 0 revealed a doublet
conformations in solution[ However\ calculations ð01Ł
suggest the energy di}erence between ring conformations
is too low for this to be a realistic possibility at room
temperature[ Unfortunately no platinum satellites could
be con_dently resolved or assigned for any of the spectra[
2 was studied by variable temperature 20P NMR "d5!
DMSO#[ The two AX type spectra observed for 2 were
partially resolved in d5!DMSO at 187 K whilst at 227 K
the signals coalesced "Fig[ 2#[
The X!Ray structure of 2 reveals "Table 3\ Fig[ 2# it to
be a typical square planar complex with the MS1P1N ring
adopting a distorted boat formation[ Interestingly the
PdÐS"0# bond at 1[214"0# Aý is shorter than the PdÐS"1#
bond\ whereas the S"0#ÐP"0# bond at 1[196"0# Aý is longer
than the S"1#ÐP"1# bond\ and the P"0#ÐN"0# bond is
slightly ð9[917 AýŁ longer than the P"1#ÐN"0# bond of
0[455"2# Aý[ One could speculate that the electron with!
drawing e}ect of the ethoxy substituents causes the S"1#Ð
P"1# and P"1#ÐN"0# bonds to be slightly shorter[ The PdÐ
SÐP bond angles are 090[98"4# and 009[97"4#> and the SÐ
PÐN angles are 005[6"0# and 006[3"0#> whilst the PÐNÐP
angle is 014[0"1#> as expected for a square planar distorted
boat type structure ð00Ł[
1
as expected "52[4\ 41[5 ppm\ J"20P!20P# ꢁ11 Hz# for the
two inequivalent phosphorus environments[
By X!ray crystallography 0 exists as a cisoid "w[r[t the
P1S bonds# dimer in the solid state "Table 2\ Fig[ a0#\
the phosphorus with the phenyl substituents being pen!
dant thus reducing any steric crowding[ The SP [[[ PS
torsion angle is 76[9> which is comparable to the cisoid
iPr1P"S#NHP"S#PiPr1 ð68>Ł ð00Ł[ The P"0#ÐS"0# bond
Ä
length at 0[826"0# A is considerably longer than the pen!
dant P"1#ÐS"1# bond length of 0[819"1# as a consequence
of S"0# being involved in S [[[ HÐN hydrogen!bonding[
The PÐN bond lengths and the PÐNÐP bond angle
ð018[8"1#>Ł are normal "Fig[ 1#[
Znð"EtO#1P"S#NP"S#Ph1Ł1 "1# was obtained by re~uxing
zinc chloride with two molar equivalents of KOtBu and
In contrast to 2 in 3 "Fig[ 3#\ one MS1P1N ring adopts

203
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D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
204
Table 1
Chemical shifts and 1J"20P!20P# coupling constants in 20P NMR "CDCl2# for "EtO#1P"S#NHP"S#Ph1 and
Mð"EtO#1P"S#NHP"S#Ph1Ł1 "MꢁZn\ Pd\ Pt#] P0 denotes the ethoxy and P1 denotes the phenyl substituted phos!
phorus atoms
d:ppm
1J"20P!20P#:Hz
ðP0!P1Ł
P0
P1
"EtO#1P"S#NP"S#Ph1 0
52[5
35[8
42[2
25[2
11[9
15[3
Znð"EtO#1P"S#NP"S#Ph1Ł1 1
Pdð"EtO#1P"S#NP"S#Ph1Ł1 2
Ptð"EtO#1P"S#NP"S#Ph1Ł1 3
49[4
33[1
39[4
26[7
49[3
33[0
39[8
27[2
16[4
14[5
15[6
14[2
Table 2
a distorted boat conformation and the other MS1P1N
ring adopts a chair formation\ so both known con!
formations of the MS1P1N ring for are observed in the
same compound[ Comparing values for the boat and
chair conformations in the molecule Table 3\ the only
signi_cant bond length di}erence is between the PÐN
Ä
Selected bond lengths "A# and angles "># for "EtO#1P"S# NHP"S#Ph1
0
"EtO#1P"S# NHP"S#Ph1
S"0#ÐP"0#
S"1#ÐP"1#
P"0#ÐN"0#
P"1#ÐN"0#
S"0#ÐP"0#ÐN"0#
S"1#ÐP"1#ÐN"0#
P"0#ÐN"0#ÐP"1#
SÐP [[[ PÐS"1#
N"0#ÐH"0n#
0[826"0#
0[819"1#
0[570"2#
0[556"2#
Ä
bonds where the P"1#ÐN"0# length is 9[0 A less than P"0#Ð
N"0# in the boat conformation whereas the PÐN bonds
are very nearly equal for the chair part of the molecule[
The most characteristic di}erence between the two con!
formations is in the bond angles[ The MÐSÐP angles for
the boat conformation are 094Ð001> as opposed to 099Ð
091> for the chair conformation[ The SÐPÐN angles are
all very similar at 005Ð019> in contrast to the SÐMÐS
angles which di}er quite greatly between all three rings
in 2 and 3[ The MÐSÐP angles are slightly smaller for 2
at 090Ð009> compared to 094Ð001> for 3[
005[2"0#
001[8"0#
018[8"1#
76[9
0[952"1#
The 20P NMR of 4 reveals an ABCD type spectrum
"Fig[ 4\ Table 4\ the values given in Table 4 were checked
using an NMR simulation program# with 2J"20P!20P#
couplings which was not observed for "Pt"PMe2#1ðN!
"iPr1PS#1Ł#¦[ PA\ PB and PC all give well resolved doublets
of triplets\ though the platinum satellites were partially
2
obscured for PA and PB[ Cis J"20P!20P# coupling was
found to be of equal magnitude to trans2J"20P!20P# coup!
ling for PA and PB[ Despite the partial overlap of the
triplets in the PD signal seven peaks are observed and the
di}erence between the 2J"20PD!20PB# trans and the 2J"20PD!
20PA# cis coupling constants is apparent[ It is interesting
1
to note the di}erence of 7 Hz between the J"20PA!084Pt#
and 1J"20PA!084Pt# coupling constants as a consequence of
the di}erent electronic e}ects of the substituent groups
on PA and PB[ This e}ect could also be explained by the
PtÐSÐP bond angles "PtÐSÐPA 097[0>\ PtÐSÐPB 86[2>#[
Given that a larger angle may imply a greater proportion
of s character in the hybridised sulfur\ this greater pro!
portion of s character is likely to increase the magnitude
of the platinum!phosphorus coupling ð05Ł[
In the structure of the square planar bis"tri!
methylyphosphine#platinum complex 4 "Fig[ 5\ Table 5#
the PtS1P1N ring shows attributes that have been
Fig[ 0[ Crystal structure of "EtO#1P"S#NHP"S#Ph1 0 showing the H!
bonded dimer[

205
D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
Fig[ 1[ 20P!"0H# VT NMR spectra "25[1 MHz# of Pdð"EtO#1P"S#NP"S#Ph1Ł1[
Table 3
Selected bond lengths "A# and angles "># for Mð"EtO#1P"S#NHP"S#Ph1Ł1 "M ꢁ Pd2\ Pt 3#
Ä
2
3
Boat
Boat
1[227"3#
Chair
1[229"3#
MÐS"0#
1[2149"8#
MÐS"2#
MÐS"1#
S"0#ÐP"0#
S"1#ÐP"1#
P"0#ÐN"0#
1[234"0#
1[916"0#
1[900"0#
0[483"2#
0[455"2#
70[55"2#
009[97"4#
090[98"4#
005[6"0#
006[3"0#
014[0"1#
1[229"3#
1[917"5#
1[997"5#
0[59"0#
0[38"1#
099[3"0#
094[1"1#
000[8"1#
005[0"5#
007[0"5#
016[7"8#
MÐS"3#
S"2#ÐP"2#
S"3#ÐP"3#
P"2#ÐN"1#
1[228"3#
1[196"4#
1[997"5#
0[59"0#
0[46"0#
81[7"0#
090[7"1#
88[4"1#
005[3"4#
008[8"4#
014[0"6#
P"1#ÐN"0#
P"3#ÐN"1#
S"0#ÐMÐS"1#
MÐS"0#ÐP"0#
MÐS"1#ÐP"1#
S"0#ÐP"0#ÐN"0#
S"1#ÐP"1#ÐN"0#
P"0#ÐN"0#ÐP"1#
S"2#ÐMÐS"3#
MÐS"2#ÐP"2#
MÐS"3#ÐP"3#
S"2#ÐP"2#ÐN"1#
S"3#ÐP"3#ÐN"1#
P"2#ÐN"1#ÐP"3#

D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
206
Fig[ 2[ Crystal structure of Pdð"EtO#1P"S#NP"S#Ph1Ł1 2[
Table 4
20P NMR parameters for "Pt"PMe2#1ð"EtO#1P"S#NP"S#Ph1Ł#¦BPh−3
d:ppm
ðJ"P!P#Ł:Hz
ðJ"P!Pt#Ł:Hz
Pt
PA
PB
PC
PD
PA
PB
34[8
23[2
Ð
14[7
54[3
46[4
Ð
PC −08[7
PD −07[9
6[8 8[8
6[8 8[8
Ð
10[7
2093[2
2951[6
Ð
observed in square planar {chair|\ {boat| and tetrahedral
complexes[ The PtÐS bond lengths di}er from each other
Ä
Ä
by 9[91 A and are 9[92Ð9[94 A longer than those in 3[ The
di}erence in PtÐSÐP angles is signi_cant\ PtÐS"0#ÐP"0# at
86[2"0#> is consistent with a {chair| type conformation
Fig[ 3[ Crystal structure of Ptð"EtO#1P"S#NP"S#Ph1Ł1 3[

207
D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
Fig[ 4[ 20P!"0H#NMR spectrum "050[86 MHz# of Pt"PMe2#1ð"EtO#1P"S#NP"S#Ph1Ł#¦BPh−3 [

D[C[ Cupertino et al[ : Polyhedron 07 "0888# 200Ð208
208
Table 5
Ä
Selected bond lengths "A# and angles "># for "Pt"PMe2#1ð"EtO#1
P"S#NP"S#Ph1Ł#BPh3 4
Bond lengths
Bond angles
PtÐS"0#
PtÐS"1#
PtÐP"2#
PtÐP"3#
S"0#ÐP"0#
S"1#ÐP"1#
P"0#ÐN"0#
P"1#ÐN"0#
1[260"2#
1[284"2#
1[153"2#
1[165"2#
1[915"3#
0[876"4#
0[597"8#
0[411"09#
S"0#ÐPtÐS"1#
PtÐS"0#ÐP"0#
PtÐS"1#ÐP"1#
S"0#ÐP"0#ÐN"0#
S"1#ÐP"1#ÐN"0#
P"0#ÐN"0#ÐP"1#
S"0#ÐPtÐP"3#
S"1#ÐPtÐP"2#
P"2#ÐPtÐP"3#
77[6"0#
86[2"0#
097[0"1#
005[3"3#
019[0"3#
021[9"5#
89[8"0#
75[3"0#
83[5"0#
for the PtS1P1N ring whereas the PtÐS"1#ÐP"1# angle of
097[0"1#> implies a {boat| type conformation[ Fur!
thermore the large angles of S"1#ÐP"1#ÐN"0# at 019[0"3#>
and P"0#ÐN"0#ÐP"1# at 021[9"5#> are more consistent with
a tetrahedral {boat| type MS1P1N ring conformation
rather than any sort of square planar complex[ In this
case the PtS1P1N ring can only be described as
puckered[
Fig[ 5[ Crystal structure of "Pt"PMe2#1ð"EtO#1P"S#NP"S#Ph1Ł#¦ in 4[
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