Hydrogen-bonded adducts formed from platinum(II) and palladium(II) thiosalicylate complexes [(Ph3E)2M(SC6H4CO2)] (E=P, As) and triethylammonium or pyridinium ions; X-ray crystal structure of [(Ph

Article abstract of DOI:10.1016/S0020-1693(02)01380-4

One-pot reactions of [MCl₂(cod)] (cod=cyclo-octa-1,5-diene; M=Pt, Pd) with two equiv of PPh₃ or AsPh₃, one equiv of thiosalicylic acid, and an excess of triethylamine base, followed by the addition of excess Na[BPh₄

Full text of DOI:10.1016/S0020-1693(02)01380-4

Inorganica Chimica Acta 346 (2003) 7Á11
/
www.elsevier.com/locate/ica
Hydrogen-bonded adducts formed from platinum(II) and
palladium(II) thiosalicylate complexes [(Ph3E)2M(SC6H4CO2)]
(Eꢀ
/
P, As) and triethylammonium or pyridinium ions;
X-ray crystal structure of [(Ph3P)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ
William Henderson *, Brian K. Nicholson
Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand
Received 28 April 2002; accepted 23 September 2002
Abstract
One-pot reactions of [MCl2(cod)] (codꢀ
/
cyclo-octa-1,5-diene; MꢀPt, Pd) with two equiv of PPh3 or AsPh3, one equiv of
/
thiosalicylic acid, and an excess of triethylamine base, followed by the addition of excess Na[BPh4] to the hot reaction mixture gives
complexes [(Ph3E)2M(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (Eꢀ
/
P, As). Analogous pyridinium and platinumÁthioglycolate
/
[(Ph3P)2Pt(SCH2CO2)] derivatives were also prepared. An X-ray crystal structure determination on [(Ph3P)2Pt-
(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ reveals hydrogen-bonding between the NH proton and the carbonyl group of the thiosalicylate
ligand, the major effect of which is to flatten the platinumÁthiosalicylate moiety. NMR spectroscopic data indicate that the
/
hydrogen-bonding interaction persists in solution.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Platinum(II) complexes; palladium(II) thiosalicylate complexes; Crystal structures
1. Introduction
reaction of [MCl2(cod)] with one equivalent of PPh3
and an excess of a nitrogen donor base (L), such as
pyridine (and derivatives thereof) and imidazole.[5] In
this contribution, we describe the synthesis of crystal-
line, hydrogen-bonded adducts of the platinum(II) and
palladium(II) complexes [(Ph3E)2M(SC6H4CO2)] (1,
We have recently reported the syntheses of a series of
thiosalicylate complexes of platinum(II), palladium(II),
and nickel(II), of the general type [L2M(SC6H4CO2)],
formed by the reaction of a metal dichloride (or in the
case of nickel, diacetate) complex [L2MCl2] with thio-
salicylic acid (2-sulfanylbenzoic acid) and pyridine base
[1]. These complexes act as metalloligands (through
sulfur) to mercury(II) halides [2]. Subsequently, Thomas
and Darkwa have synthesised the complex [(dppe)Ni-
Mꢀ
/
Pt; 2, Mꢀ
/
Pd; EꢀP, As) and [(Ph3P)2Pt-
/
(SCH2CO2)] with triethylammonium and pyridinium
cations.
(SC6H4CO2)] (dppeꢀPh2PCH2CH2PPh2) from [(dppe)-
/
2. Results and discussion
NiCl2] and thiosalicylic acid with triethylamine base [3].
Another report of the synthesis of this complex has
appeared [4]. We have also prepared a series of mixed-
ligand platinum(II) and palladium(II) thiosalicylate
complexes of the type [(Ph3P)(L)M(SC6H4CO2)] by
2.1. Synthesis and characterization
The one-pot reactions of the complexes [MCl2(cod)]
(Mꢀ
/
Pt, Pd; codꢀcyclo-octa-1,5-diene) with two
/
equivalents of PPh3, one equivalent of thiosalicylic
acid and an excess of triethylamine in refluxing metha-
* Corresponding author. Tel.: ꢁ
4219.
E-mail address: w.henderson@waikato.ac.nz (W. Henderson).
/
64-7-856-2889; fax: ꢁ64-7-838-
/
nol results in the formation of clear yellow (Pt) or redÁ
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 1 3 8 0 - 4

8
W. Henderson, B.K. Nicholson / Inorganica Chimica Acta 346 (2003) 7Á11
/
orange (Pd) solutions. When an excess of solid sodium
tetraphenylborate is added to these hot solutions,
microcrystalline solids 3a and 3b are rapidly precipi-
tated. On the basis of NMR spectroscopy, electrospray
mass spectrometry, and elemental analysis, these pro-
ducts are formulated as hydrogen-bonded adducts of the
thiosalicylate complexes [(Ph3P)2M(SC6H4CO2)Á Á ÁHN-
Et3]ꢁ[BPh4]ꢂ. The triphenylarsine complex [(Ph3As)2-
Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3c), the pyridinium
and coupling constant occurring for the PPh3 ligand
trans to the carboxylate ligand. The carbonyl CO
resonance is shifted from d 166.5 in [(Ph3P)2Pt-
(SC6H4CO2)] [1] to d 169 in the Et3NHꢁ adduct 3a,
and in a mixture of [(Ph3P)2Pt(SC6H4CO2)] with excess
[Et3NH]Cl. These data indicate that the hydrogen-
bonding interaction persists in solution, and that it
most likely involves the carboxylate group.
The positive-ion electrospray (ES) mass spectra of the
triethylammonium adducts show adduct ions with both
Hꢁ and the Et3NHꢁ cation at a relatively low cone
compounds
(3d, Mꢀ
[(Ph3P)2M(SC6H4CO2)Á Á ÁHpy]ꢁ[BPh4]ꢂ
/
Pt; 3e, MꢀPd), and the thioglycolate deriva-
/
tive [(Ph3P)2Pt(SCH2CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (4) can
be prepared in the same way. The attempted synthesis of
the triphenylarsine palladium analogue [(Ph3As)2Pd-
(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ gave a deep brown
solution, from which no product could be isolated.
The use of excess triphenylphosphine in the synthesis of
the platinum complex 3a does not influence the purity of
voltage (20 V). In contrast, no [Mꢁ
observed for the pyridinium complexes, though [Mꢁ
H]ꢁ and weak [MꢁEt3NH]ꢁ ions (due to adventitious
Et3NHꢁ in the spectrometer) were observed. For
example, for 3a the ions [(Ph3P)2Pt(SC6H4CO2)ꢁ
H]ꢁ
(m/z 872, 100%) and [(Ph3P)2Pt(SC6H4CO2)ꢁ
Et3NH]ꢁ
/
pyH]ꢁ ions were
/
/
/
/
(m/z 973, 80%) were both observed at 20 V. However, at
50 V, the only ion observed was [(Ph3P)2Pt(SC6H4CO2)
the product formed, however for the palladiumÁ
nylphosphine complexes, use of excess PPh3 in the
synthesis results in observation of free PPh3 (d ꢂ5) in
the 31PÁ{1H} NMR spectra of the isolated products,
/triphe-
ꢁ
H]ꢁ, while at 5 V the Et3NHꢁ adduct ion dominated.
/
/
Interestingly, for the thioglycolate adduct 4 only a [Mꢁ
/
/
Et3NH]ꢁ ion (m/z 911) was seen at 20 V, suggesting
that the interaction between the platinum complex
[(Ph3P)2Pt(SCH2CO2)] and Et3NHꢁ is stronger than
that between the cation and the thiosalicylate com-
plexes, possibly due to greater steric accessibility and/or
basicity of the (aliphatic) carbonyl group. The presence
of the [BPh4]ꢂ ion was confirmed in 3a from the
negative ion ES spectrum, which showed a single intense
peak at m/z 319.
and the PPh3 ligand trans to S was seen to be
broadened, presumably due to exchange with the free
PPh3. The palladium complexes were therefore synthe-
sised using a stoichiometric amount of the phosphine
ligand.
Interestingly, no immediate precipitation of [Et3NH]-
[BPh4] is observed when solid Na[BPh4] is added to a hot
solution of triethylammonium chloride under analogous
conditions. This suggests that the hydrogen-bonding
interaction with the platinum complex, and the presence
of a bulky cation-bulky anion combination are required
for crystallisation of the adduct.
Complexes 3 and 4 are insoluble in water and diethyl
ether, are only sparingly soluble in methanol, but are
soluble (particularly the triethylammonium adducts) in
chloroform and dichloromethane. Melting points are
lower than for the parent thiosalicylate complexes, and
melting occurs with gas evolution, presumably libera-
tion of triethylamine or pyridine.
The 1H NMR spectrum of 3a shows the expected
resonances due to the triethylammonium cation, with
the integrated spectrum confirming the 1:1 adduct of
[(Ph3P)2Pt(SC6H4CO2)] and [Et3NH][BPh4]. Unsurpris-
ingly, solutions of the hydrogen-bonded adducts give
very similar 31PÁ
/
{1H} NMR spectra, with similar
chemical shifts and coupling constants. The complex
[(Ph3P)2Pt(SC6H4CO2)] gives two doublets in its 31PÁ
/
1
{1H} NMR spectrum, at d 24.48 and 10.15, with J
coupling to 195Pt of 2884 and 3899 Hz, respectively,
assigned to the PPh3 ligands trans to S and O,
respectively [1]. For complex 3a, values of d 24.44 and
1
9.85 were observed, with J(PtP) 2886 and 3963 Hz,
respectively, with the greatest change in chemical shift

W. Henderson, B.K. Nicholson / Inorganica Chimica Acta 346 (2003) 7Á
/
11
9
2.2. Crystal structure of
[(Ph3P)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3a)
Table 1
A comparison of structural features for free [1] and H-bonded
[(Ph3P)2Pt(SC6H4CO2)]
Previous crystallographic studies on thiosalicylate
complexes of square-planar d8 metal centres have shown
Free (1)
H-bonded (in 3a)
˚
PtÁ
PtÁ
SÁ Á ÁO (A)
PÁPtÁP (8)
Twist angle (8)
/
S (A)
2.322(2)
2.250(1)
2.99
2.296(1)
2.233(1)
3.114(2)
97.52(4)
7.6(2)
that the metalÁthiosalicylate system is very flexible, and
/
˚
/
P(1) (A)
a wide range of fold angles between the metal coordina-
tion and thiosalicylate planes have been observed. These
results have recently been summarized [5]. Since one of
the complexes structurally characterised was the com-
plex [(Ph3P)2Pt(SC6H4CO2)], a crystal structure deter-
mination was carried out on the triethylammonium
adduct 3a, to confirm the hydrogen-bonding aspect,
and to directly examine the effect of such hydrogen-
˚
/
/
100.46(4)
21.1
a
PtÁ
PtÁ
SÁ
/
O
P(2)
2.109(3)
2.303(1)
84.7(1)
47.2
2.069(2)
2.321(1)
90.9(1)
/
/
PtÁ
/
O (8)
Fold angle (8)
b
26.75(7)
a
The angle between the CO2 group plane and the plane defined by
the rest of the thiosalicylate ligand [5].
b
bonding on the platinumÁthiosalicylate system. Hydro-
/
The dihedral angle between the Pt coordination plane and the
plane of the thiosalicylate ligand [5].
gen-bonding between the triethylammonium cation and
a coordinated thiosalicylate ligand has been observed in
the dimeric anionic manganese complex [Et3NH]2[{Mn-
˚
complexes [5], the flattening of the fold angle leads to a
decrease in the angle that the carboxylate group is
twisted out of the ligand plane (21.1 and 7.68 in 1 and
3a, respectively), and an increase in the SÁ Á ÁO ‘bite’ of
(SC6H4CO2)(CO)3}2], with NÁ
/
H 0.98 A and OÁ Á ÁH 1.73
˚
A [6] and in some anionic molybdenum [7] and iron
([Et3NH][Fe(SC6H4CO2)2(2-methylimidazole)]) com-
plexes [8]. However, this is the first direct comparison
for the same molecule with and without H-bonding
interactions.
˚
the chelating ligand (2.99 to 3.11 A). The ligand is
apparently also more tightly bound in the H-bonded
form since the PtÁ
/
O and PtÁS bonds are both shortened
/
The structure of the H-bonded cation of 3a is
illustrated in Fig. 1. There is the usual square-planar
Pt(II) centre, with two cis-Ph3P ligands and the chelat-
ing (S,O) thiosalicylate ligand, as in the free complex [1].
In 3a there is an extra interaction involving H-bonding
˚
[2.069(2) and 2.296(1) A] relative to the same distances
˚
in the free form [2.109(3) and 2.322(2) A, respectively].
The coordination around platinum is more regularly
square in 3a with PÁ
/
PtÁ
/
P and SÁ
/
PtÁO angles of
/
97.52(4) and 90.9(1)8, respectively, compared with
100.46(4) and 84.7(1)8 in 1; however the Pt is less planar
of [Et3NH]ꢁ with the CÄ
/O of the carboxylate group.
Table 1 lists some parameters for the Pt complex in the
free (1) and H-bonded (3a) forms, which on comparison
show significant differences. The most dramatic is the
fold angle between the plane of the ligand and the Pt
coordination plane, 47.28 in 1 and 26.75(7)8 in 3a. As
seen earlier in a series of Pt, Pd and Ni thiosalicylate
˚
˚
0.02 A).
in 3a (rms deviation 9
The H-bonded interaction between the neutral Pt
complex and the [Et3NH]ꢁ cation is defined by NÁ
/
0.08 A) than in 1 (9
/
/H
˚
and HÁ Á ÁO distances of 0.93(3) and 1.79(3) A, respec-
tively, and a NÁ
HÁ Á ÁO angle of 1748, very similar to the
cationÁanion hydrogen-bonded interactions found for
/
/
the [Et3NH]ꢁ salts of the manganese and molybdenum
thiosalicylate complexes mentioned earlier [6,7], though
the equivalent interaction is more bent (1588) in
[Et3NH][Fe(SC6H4CO2)2(2-methylimidazole)] [8].
The packing in the crystal of 3a is clearly assisted by a
series of edge-face phenyl ‘embraces’ between the PPh3
groups and the [BPh4]ꢂ anions, with BÁ Á ÁP distances of
˚ ˚
7.6Á7.7 A compared with that of 7.1 A found for
/
[Ph4P][BPh4] [9]. The network of these interactions is
complicated but is related to those analysed in detail for
other systems (particularly [PPh4]ꢁ salts) by Scudder
and Dance [10].
Although not the original intention of this work,
[Et3NH][BPh4] acts as an ionic crystallizing aid for
neutral thiosalicylate complexes which bear a hydrogen-
bond accepting CÄ
/
O group, and might find application
in the crystallization of other H-bond accepting com-
Fig.
1. Molecular
structure
of
the
cation
[(Ph3P)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ of 3a [as its BPh4ꢂ salt] showing
the atom numbering scheme.
plexes which are difficult to crystallize.

10
W. Henderson, B.K. Nicholson / Inorganica Chimica Acta 346 (2003) 7Á11
/
3. Experimental
1J(PtP) 3963 Hz, P trans to O]; 1H NMR, d 7.7Á
6.8 (m,
/
54H, Ph), 2.09 [q, CH2 of Et3NHꢁ, J(HH) 7 Hz] and
3.1. Instrumentation
0.66 [t, CH3 of Et3NHꢁ, J(HH) 7 Hz].
All NMR spectra were recorded in CDCl3 solution on
a Bruker AC300P instrument, as follows: 1H (300.13
3.4. Synthesis of
[(Ph3P)2Pd(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3b)
MHz), 13C (75.47 MHz), 31P (121.51 MHz). 1H and 13
C
NMR spectra were referenced relative to external SiMe4
(d 0.0), while 31P NMR spectra were referenced relative
to external 85% H3PO4 (d 0.0). Electrospray mass
spectra were recorded on a VG Platform II instrument,
using methanol as the mobile phase and solvent. Assign-
ment of major ions was aided by use of the ISOTOPE
program [11] and m/z values quoted are for the most
intense peak in the isotope distribution envelope of the
Following the method above for 3a, [PdCl2(cod)] (200
mg, 0.701 mmol), triphenylphosphine (368 mg, 1.404
mmol), thiosalicylic acid (108 mg, 0.701 mmol) and
triethylamine (1 ml, excess) gave a bright red solution.
Solid Na[BPh4] (239 mg, 0.699 mmol) was added to the
refluxing solution, resulting in the immediate precipita-
tion of orange microcrystals. Yield 557 mg, 66%. M.p.
180Á
for C73H70NBO2P2PdS: C, 72.8; H, 5.9; N, 1.2%. ES
MS: cone voltage 20 V, [(Ph3P)2Pd(SC6H4CO2)ꢁ
H]ꢁ
(m/z 783, 75%), [(Ph3P)2Pd(SC6H4CO2)ꢁ
Et3NH]ꢁ
/
182 8C. Anal. Found: C, 72.6; H, 5.8; N, 1.2. Calc.
ion. Melting points were recorded on a ReichertÁJung
/
hotstage apparatus, and are uncorrected.
/
/
3.2. Materials and methods
(m/z 884, 55%).
Reactions were carried out in air, in reagent grade
methanol, with no further purification. Water was singly
distilled prior to use; diethyl ether was of LR grade and
used as supplied. The following compounds were used as
supplied from commercial sources: K2[PtCl4] (Johnson
Matthey), thiosalicylic acid (Sigma), thioglycolic acid
(BDH), triphenylphosphine (BDH), triphenylarsine
(Koch-Light), triethylamine (BDH), triethylammonium
chloride (BDH), pyridine (BDH), and sodium tetraphe-
nylborate (BDH). The complexes [PtCl2(cod)] [12] and
[PdCl2(cod)] [13] were prepared by the literature meth-
ods.
3.5. Synthesis of
[(Ph3As)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3c)
Following the method above for 3a, [PtCl2(cod)] (200
mg, 0.535 mmol), triphenylarsine (491 mg, 1.604 mmol),
thiosalicylic acid (83 mg, 0.539 mmol) and triethylamine
(1 ml, excess) in methanol (20 ml) gave a clear bright
yellow solution. Addition of solid Na[BPh4] (200 mg,
0.585 mmol) gave yellow microcrystals. Yield 574 mg,
78%. M.p. 193Á196 8C. Anal. Found: C, 63.3; H, 5.0; N,
/
1.15. Calc. for C73H70NAs2BO2PtS: C, 63.5; H, 5.1; N,
1.0%. ES MS: cone voltage 20 V, [(Ph3As)2Pt-
(SC6H4CO2)ꢁ
/
H]ꢁ (m/z 960, 65%), [(Ph3As)2Pt-
Et3NH]ꢁ (m/z 1061, 100%).
3.3. Synthesis of
[(Ph3P)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3a)
(SC6H4CO2)ꢁ
/
3.6. Synthesis of
[(Ph3P)2Pt(SC6H4CO2)Á Á ÁHpy]ꢁ[BPh4]ꢂ (3d)
A mixture of [PtCl2(cod)] (200 mg, 0.535 mmol),
triphenylphosphine (440 mg, 1.679 mmol), thiosalicylic
acid (83 mg, 0.539 mmol) and triethylamine (1 ml,
excess) in methanol (20 ml) was heated to reflux for 10
min giving a clear, bright yellow solution. Solid
Na[BPh4] (220 mg, 0.643 mmol) was added to the
refluxing solution, resulting in the immediate precipita-
tion of yellow microcrystals. After cooling and standing
for 12 h, the solid was filtered, washed with cold
methanol (5 ml), water (10 ml), methanol (5 ml) and
Following the method for 3a,
a mixture of
[PtCl2(cod)] (200 mg, 0.535 mmol), triphenylphosphine
(280 mg, 1.069 mmol), thiosalicylic acid (83 mg, 0.539
mmol) and pyridine (1 ml, excess) in methanol (20 ml),
gave a clear, bright yellow solution. Solid Na[BPh4] (250
mg, 0.731 mmol) was added to the refluxing solution,
resulting in the immediate precipitation of yellow
microcrystals. Yield 667 mg, 98%. M.p. 162Á
/
165 8C.
diethyl ether (2ꢃ
562 mg, 81%. M.p. 182Á
H, 5.5; N, 1.1; S, 2.4. Calc. for C73H70NBO2P2PtS: C,
67.8; H, 5.5; N, 1.1; S, 2.5%. ES MS: positive ion, cone
voltage 20 V, [(Ph3P)2Pt(SC6H4CO2)ꢁ
100%), [(Ph3P)2Pt(SC6H4CO2)ꢁ
Et3NH]ꢁ (m/z 973,
80%). Cone voltage 50 V, [(Ph3P)2Pt(SC6H4CO2)ꢁ
H]ꢁ (m/z 872, 100%). Negative ion, cone voltage 20
V, [BPh4]ꢂ (m/z 319, 100%). 31PÁ{1H} NMR, d 24.4 [d,
1J(PtP) 2886 Hz, 2J(PP) 22 Hz, P trans to S], and 9.9 [d,
/
5 ml) and dried under vacuum. Yield
Anal. Found: C, 69.0; H, 4.9; N, 1.4. Calc. for
C72H60NBO2P2PtS: C, 68.0; H, 4.8; N, 1.1%. 31PÁ
/
186 8C. Anal. Found: C, 67.7;
/
{1H} NMR, d 23.9 [d, J(PtP) 2840 Hz, J(PP) 21 Hz]
1
2
1
and 10.5 [d, J(PtP) 3978 Hz].
/
H]ꢁ (m/z 872,
/
3.7. Synthesis of
[(Ph3P)2Pd(SC6H4CO2)Á Á ÁHpy]ꢁ[BPh4]ꢂ (3e)
/
/
Following the method for 3a, a mixture of
[PdCl2(cod)] (200 mg, 0.701 mmol), triphenylphosphine

W. Henderson, B.K. Nicholson / Inorganica Chimica Acta 346 (2003) 7Á
/
11
11
(367 mg, 1.401 mmol), thiosalicylic acid (109 mg, 0.708
mmol) and pyridine (1 ml, excess) in methanol (30 ml),
4. Supplementary material
gave a clear, redÁ
mg, 0.699 mmol) was added to the refluxing solution,
resulting in the immediate formation of orange micro-
crystals. Yield 680 mg, 82%. M.p. 159Á161 8C. Anal.
Found: C, 72.9; H, 5.0; N, 1.3. Calc. for
C72H60NBO2P2PdS: C, 73.1; H, 5.1; N, 1.2%.
/
orange solution. Solid Na[BPh4] (239
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 192640 for compound 3a.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
/
Cambridge, CB2 1EZ, UK (fax: ꢁ44-1223-336-033;
/
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
3.8. Synthesis of
[(Ph3P)2Pt(SCH2CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (4)
A mixture of [PtCl2(cod)] (200 mg, 0.535 mmol),
triphenylphosphine (280 mg, 1.069 mmol), thioglycolic
acid (10 drops, excess) and triethylamine (1 ml, excess)
was heated to reflux for 10 min in methanol (20 ml),
giving a clear, bright yellow solution. Solid Na[BPh4]
(183 mg, 0.535 mmol) was added to the refluxing
solution. On cooling, pale yellow microcrystals were
deposited, which were filtered, washed with methanol (5
ml), water (5 ml), methanol (5 ml), and diethyl ether (5
ml), and dried under vacuum. Yield 165 mg, 25%. M.p.
Acknowledgements
We thank the University of Waikato for financial
support of this work. The New Zealand Lottery Grants
Board is thanked for a grant in aid towards the mass
spectrometer, and the generous loan of platinum from
Johnson Matthey plc is acknowledged. Professor Ward
Robinson and Dr. Jan Wikaira (University of Canter-
bury) are thanked for collection of the X-ray data set.
187Á
/
191 8C. Anal. Found: C, 66.6; H, 5.6; N, 1.1. Calc.
for C68H68NBO2P2PtS: C, 66.3; H, 5.6; N, 1.1%. ES MS:
cone voltage 20 V, [(Ph3P)2Pt(SCH2CO2)ꢁ
Et3NH]ꢁ
/
(m/z 911, 55%). 31PÁ
2871 Hz, J(PP) 22 Hz] and 11.8 [d, J(PtP) 3795 Hz].
/
{1H} NMR, d 22.1 [d, 1J(PtP)
2
1
References
3.9. X-ray crystal structure of
[(Ph3P)2Pt(SC6H4CO2)Á Á ÁHNEt3]ꢁ[BPh4]ꢂ (3a)
[1] L.J. McCaffrey, W. Henderson, B.K. Nicholson, J.E. Mackay,
M.B. Dinger, J. Chem. Soc. Dalton Trans. (1997) 2577.
[2] L.J. McCaffrey, W. Henderson, B.K. Nicholson, Polyhedron 17
(1998) 221.
Crystals of 3a were obtained from CH2Cl2ÁEt2O.
/
[3] M.S. Thomas, J. Darkwa, Polyhedron 17 (1998) 1811.
[4] B.-S. Kang, Z.-N. Chen, H.-R. Gao, Z.-Y. Zhou, B.-M. Wu,
T.M.C. Mak, Z. Lin, Acta Chim. Sin. 56 (1998) 58; Chem. Abstr.
128 (1998) 175338e.
Crystal and intensity data were collected on a Siemens
SMART CCD diffractometer using standard procedures.
An empirical correction for absorption was carried out
with SADABS [14]; all other calculations were carried out
with the SHELX-97 programs [15]. Refinement was based
on F2. One of the ethyl groups of the [Et3NH]ꢁ cation
was disordered, with the CH2 carbon over two equal
sites. The hydrogen atoms were included in calculated
positions, except for those on the disordered group,
which were omitted.
[5] W. Henderson, L.J. McCaffrey, B.K. Nicholson, J. Chem. Soc.
Dalton Trans. (2000) 2753.
[6] C.V. Depree, L. Main, B.K. Nicholson, K. Roberts, J. Organo-
met. Chem. 517 (1996) 201.
[7] (a) J. Li-Kao, O. Gonza´lez, R. Mariezcurrena, R. Baggio, M.T.
Garland, D. Carillo, Acta Crystallogr. C 51 (1995) 2486;
(b) J. Li-Kao, O. Gonza´lez, R. Baggio, M.T. Garland, D. Carillo,
Acta Crystallogr. C 51 (1995) 575.
[8] J.S. Bashkin, J.C. Huffman, G. Christou, J. Am. Chem. Soc. 108
(1986) 5038.
3.9.1. Crystal data
C73H70BNO2P2PtS, Mr 1293.2, triclinic, space group
[9] M.A. Lloyd, C.P. Brock, Acta Crystallogr. Sect. B 53 (1997) 773.
[10] M. Scudder, I. Dance, J. Chem. Soc. Dalton Trans. (1998) 3155
and references therein.
˚
¯
P1, aꢀ
/
13.487(6), bꢀ
70.543(4), gꢀ
1.408 g cmꢂ3, Zꢀ
Ka) 2.435 mmꢂ1, Tmax, min 1.000, 0.772. A total of
40 049 reflections, 12 970 unique (Rint 0.0306) were
collected at 163 K, for 2Bu B278. Final R1ꢀ0.0261
[I ꢀ2s(I)], wR2ꢀ0.0671 (all data), GoFꢀ1.059, final
De ꢁ1.21/ꢂ1.50.
/
14.525(6), cꢀ
89.399(4)8, Uꢀ
2, F(000) 1320, m(Mo
/
17.372(7) A, aꢀ
/
72.749(4), bꢀ
/
/
/3050(2)
[11] L.J. Arnold, J. Chem. Educ. 69 (1992) 811.
[12] J.X. McDermott, J.F. White, G.M. Whitesides, J. Am. Chem.
Soc. 98 (1976) 6521.
3
˚
A , Dcalc
ꢀ
/
/
[13] D. Drew, J.R. Doyle, Inorg. Synth. 13 (1972) 52.
[14] R.H. Blessing, Acta Crystallogr. A 51 (1995) 33.
[15] G.M. Sheldrick, SHELX-97, Programs for the Solution and
ꢀ
/
/
/
/
/
/
/
Refinement of Crystal Structures, University of Gottingen,
¨
/
/
Gottingen, Germany, 1997.
¨