Further studies on the coordination chemistry of [Pt2(μ-S) 2(PPh3)4] towards indium(III) substrates

Article abstract of DOI:10.1016/j.ica.2011.05.014

The reactivity of the metalloligand [Pt₂(μ-S) ₂(PPh₃)₄] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO₃) ₃ and halide (KBr or NaI) gave the four-coordinate adducts [Pt ₂(μ-S)₂(PPh₃)₄InX ₂]⁺[InX₄]^- (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt ₂(μ-S)₂(PPh₃)₄] with indium(III) chloride was more complex; the ion [Pt₂(μ-S)₂(PPh ₃)₄InCl₂]⁺ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh ₄^- salt. Analysis of [Pt₂(μ-S) ₂(PPh₃)₄InCl₂]⁺[BPh ₄]^- by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt₂(μ-S) ₂(PPh₃)₄InCl(OMe)}₂]²⁺ (proposed to contain an In₂(μ-OMe)₂ unit with five-coordinate indium) and its fragment ion [Pt₂(μ-S) ₂(PPh₃)₄InCl(OMe)]⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with InCl ₃·3H₂O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt₂(μ-S)₂(PPh ₃)₄InQ₂]⁺, isolated as its PF ₆^- salt. The same cationic complex is formed when [Pt ₂(μ-S)₂(PPh₃)₄] is reacted with InQ₃ in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph₃P)₂PtQ]⁺ formed by disintegration of the trinuclear complex [Pt₂(μ-S) ₂(PPh₃)₄InQ₂]⁺ with byproduct Q^-. [(Ph₃P)₂PtQ]⁺BPh ₄^- was independently prepared from cis-[PtCl ₂(PPh₃)₂] and HQ/Me₃N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.

Full text of DOI:10.1016/j.ica.2011.05.014

Inorganica Chimica Acta 375 (2011) 248–255
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Further studies on the coordination chemistry of [Pt2(l-S)2(PPh3)4] towards
indium(III) substrates
b
William Henderson a, , Allen G. Oliver
⇑
a Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton 3240, New Zealand
b Molecular Structure Facility, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
The reactivity of the metalloligand [Pt2(l-S)2(PPh3)4] towards a variety of indium(III) substrates has been
Received 18 February 2011
Accepted 11 May 2011
Available online 1 June 2011
explored. Reaction with excess In(NO3)3 and halide (KBr or NaI) gave the four-coordinate adducts
[Pt2(
l
-S)2(PPh3)4InX2]+[InX4]ꢀ (X = Br, I). An X-ray structure determination on the iodo complex revealed
a
slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of
[Pt2(
l-S)2(PPh3)4] with indium(III) chloride was more complex; the ion [Pt2(
l
-S)2(ꢀPPh3)4InCl2]+ was
Keywords:
Platinum complexes
Indium complexes
Sulfide ligands
Crystal structure
initially observed in solution (using ESI mass spectrometry), and isolated as its BPh4 salt. Analysis of
[Pt2(
However in solutions containing methanol, partial solvolysis occurred to give the di-indium species
[{Pt2( -OMe)2 unit with five-coordinate indium)
-S)2(PPh3)4InCl(OMe)}2]2+ (proposed to contain an In2(
and its fragment ion [Pt2(
-S)2(PPh3)4InCl(OMe)]+. Reaction of [Pt2(
8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt2(
isolated as its PF6 salt. The same cationic complex is formed when [Pt2(
l
-S)2(PPh3)4InCl2]+[BPh4]ꢀ by ESI MS showed the parent cation when analysed in MeCN solution.
l
l
l
l
-S)2(PPh3)4] with InCl3ꢁ3H2O,
Electrospray ionisation mass spectrometry
Ligand exchange reactions
l
-S)2(PPh3)4InQ2]+,
ꢀ
l
-S)2(PPh3)4] is reacted with
InQ3 in methanol, but in this case the product is contaminated with the mononuclear complex
[(Ph3P)2PtQ]+ formed by disintegration of the trinuclear complex [Pt2( -S)2(PPh3)4InQ2]+ with byproduct
l
Qꢀ. [(Ph3P)2PtQ]+BPh4ꢀ was independently prepared from cis-[PtCl2(PPh3)2] and HQ/Me3N, and is the first
example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands.
Ó 2011 Elsevier B.V. All rights reserved.
-S)2(PPh3)4Tl]+ (isolated as NO3
ꢀ
1. Introduction
reacts with TlNO3 to give [Pt2(
l
ꢀ
and PF6 salts) [6], and the same behaviour is again seen with
The metalloligand properties of dinuclear platinum(II) sulfido
the dppf analogue [5]. Thallium(III) adducts [Pt2(
l
-S)2(PPh3)4
(n = 0–2) have been obtained from reaction of
-S)2(PPh3)4] with TlBr3, PhTlBr2 or Ph2TlBr [7]. Additional
studies also indicate that adducts can also be formed by related
systems, such as the selenide [Pt2( -Se)2(PPh3)4] (which forms
the four-coordinate adduct [Pt2(
-Se)2(PPh3)4InBr2]+ [8] (as well
as [Pt2(
-Se)2(PPh3)4TlPh2]+ [7], [Pt2( -Se)2(PPh3)4Ga(NO3)2]+ [8],
and [Pt2(
-Se)2(PPh3)4Tl]+ [8]). Likewise, the palladium analogue
[Pd2( -S)2(dppf)2] forms adducts including the five-coordinate in-
dium adduct [Pd2( -S)2(dppf)2InCl3], along with [Pd2( -S)2(dppf)2
GaCl2]+ and [Pd2( -S)2(dppf)2Tl]+ [9].
In this contribution we describe some new indium adducts of
[Pt2( -S)2(PPh3)4] containing a range of monodentate and chelat-
ing ligands, including a reinvestigation of adducts formed by
[Pt2( -S)2(PPh3)4] with InCl3. Indium–chalcogenide materials are
+
complexes, typified by [Pt2(l-S)2(PPh3)4] 1, are well-known [1,2].
TlBrnPh2ꢀn
]
Reactions of this complex with a variety of metal-based substrates
have provided a general synthetic methodology for the synthesis of
tri- and polymetallic sulfide-bridged aggregates. While the major-
ity of known adducts are with transition metals, main group metal
adducts are also known for a number of metals.
[Pt2(l
l
l
l
l
In the area of group 13 metal chemistry, although aluminium
l
adducts of [Pt2(l-S)2(PPh3)4] have not been reported, there are a
l
number of adducts with the heavier (and chemically softer) cong-
eners gallium, indium and thallium, which have also been studied
l
l
l
using theoretical methods [3]. Reaction of [Pt2(
InCl3 gave the neutral adduct [Pt2( -S)2(PPh3)4InCl3] 2 (which
was structurally characterised) while reaction with 2 equivalents
of GaCl3 gave the salt [Pt2(
-S)2(PPh3)4GaCl2]+[GaCl4]ꢀ [4]. The
analogous InCl3 adduct has also been prepared from [Pt2(
S)2(dppf)2] [dppf = 1,10-bis(diphenylphosphino)ferrocene] [5]. Both
l-S)2(PPh3)4] with
l
l
l
l
l
-
of technological importance for example in photovoltaic applica-
tions [10–13] and the possibility that such compounds might be
useful in the synthesis of new indium–chalcogenide materials is
thallium(I) and thallium(III) adducts are known; [Pt2(l-S)2(PPh3)4]
suggested by the reaction of [Pt2(
8H2O which yielded novel complex [{Pt2(
In2(
-Se)2]2+, containing an {In2Pt4Se6} core [14]. Our methodology
l
-Se)2(PPh3)4] with In(ClO4)3ꢁ
a
l
-Se)2(PPh3)4}2
⇑
Corresponding author. Fax: +64 7 838 4219.
E-mail address: w.henderson@waikato.ac.nz (W. Henderson).
l
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.05.014

W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
249
Table 1
is to apply electrospray ionisation mass spectrometry (ESI MS) to
Selected bond lengths (Å) and angles (°) for [Pt2(l-S)2(PPh3)4InI2][InI4] 3b.
characterise reaction mixtures and products in the {Pt2S2}-In
system. ESI MS is now a fully established technique for the charac-
terisation of coordination and organometallic compounds, and has
been applied to the characterisation of a number of indium
systems including organo-indium compounds [15–17], indium
trihalide solutions [18], and a variety of coordination complexes
[19–24].
Pt(1)–P(2)
Pt(1)–S(1)
Pt(2)–P(4)
Pt(2)–S(2)
In(1)–S(1)
In(1)–I(1)
2.2864(12)
2.3849(11)
2.2758(12)
2.3748(11)
2.4906(12)
2.7059(5)
Pt(1)–P(1)
Pt(1)–S(2)
Pt(2)–P(3)
Pt(2)–S(1)
In(1)–S(2)
In(1)–I(2)
2.3021(12)
2.3870(11)
2.2936(11)
2.3883(12)
2.5081(12)
2.7068(5)
P(2)–Pt(1)–P(1)
P(1)–Pt(1)–S(2)
P(4)–Pt(2)–P(3)
P(3)–Pt(2)–S(1)
S(1)–In(1)–S(2)
S(2)–In(1)–I(1)
S(2)–In(1)–I(2)
Pt(1)–S(1)–Pt(2)
99.79(4)
86.62(4)
97.74(4)
87.57(4)
77.16(4)
112.48(3)
120.60(3)
85.06(4)
P(2)–Pt(1)–S(1)
S(1)–Pt(1)–S(2)
P(4)–Pt(2)–S(2)
S(2)–Pt(2)–S(1)
S(1)–In(1)–I(1)
S(1)–In(1)–I(2)
I(1)–In(1)–I(2)
Pt(2)–S(2)–Pt(1)
92.06(4)
81.57(4)
92.94(4)
81.76(4)
123.64(3)
112.82(3)
2. Results and discussion
2.1. Chemistry of [Pt2(l-S)2(PPh3)4] with indium(III) and halide ions
108.152(18)
85.31(4)
Reactions between [Pt2(
excess of either NaBr or KI proceeded straightforwardly, with posi-
tive-ion ESI MS showing the ions [Pt2(
-S)2(PPh3)4InX2]+ (X = Br,
m/z 1777.988; X = I, m/z 1870.963) as the dominant ions in the
reaction mixtures. In the iodide case, the complex [Pt2( -S)( -I)
(PPh3)4]+ was seen as a weak ion at m/z 1598; this ion has been
found to be rather ubiquitous in reactions of [Pt2( -S)2(PPh3)4]
with metal iodide complexes [25], so its presence is not unex-
pected. On a macroscopic scale, reaction of [Pt2( -S)2(PPh3)4] with
l-S)2(PPh3)4], excess In(NO3)3 and an
[InI4]ꢀ anion:
In(2)–I(3)
2.7055(6)
In(2)–I(5)
2.7059(6)
l
In(2)–I(4)
2.7072(6)
In(2)–I(6)
2.7205(6)
I(3)–In(2)–I(5)
I(5)–In(2)–I(4)
I(5)–In(2)–I(6)
107.821(18)
109.171(17)
112.46(2)
I(3)–In(2)–I(4)
I(3)–In(2)–I(6)
I(4)–In(2)–I(6)
110.465(18)
108.543(17)
108.38(2)
l
l
l
triphenylphosphine ligands. As can be seen in Figs. 1 and 2, the
l
+
binding of the InI2 fragment to the two sulfide centres is fairly
excess In(NO3)3 proceeded rapidly in methanol, giving an almost
colourless solution. Upon addition of a large excess of either NaBr
or KI, white (Br) or pale cream (I) precipitates of the products
[Pt2(l-S)2(PPh3)4InX2][InX4] (3a X = Br; 3b X = I) were obtained in
good yields and high purities as shown by elemental microanalysis.
symmetrical, but slightly distorted by a twist between the InI2
and InS2 planes of 81.7°, compared to the value of 90° expected
for a symmetrical tetrahedral structure. The In–S bond distances
of 2.4906(12) and 2.5081(12) Å are longer than those of 2.484(1)
and 2.486(1) Å in the only other structurally characterised four-
coordinate indium complex containing an S2InI2 donor set,
N(Ph2PS)2InI2 [26]. This is presumably because the [N(Ph2PS)2]ꢀ
ligand is monoanionic and binds more strongly to In than neutral
ESI MS analysis of 3a in MeOH solution showed the expected
[Pt2(
together with a trace of [Pt2(
l
-S)2(PPh3)4InBr2]+ ion as the dominant ion at m/z 1777.988,
l
-S)2(PPh3)4InBrCl]+ (m/z 1733.036),
presumably formed from adventitious chloride ions.
1. The In–I bond distances of [Pt2(l
-S)2(PPh3)4InI2]+ [2.7068(5)
and 2.7059(5) Å] are also considerably longer than in N(Ph2PS)2InI2
[2.6768(6) and 2.6872(7) Å].
The In–S bond distances of 3b can be compared with somewhat
longer values of 2.614(2) Å in the neutral adduct [Pt2(l-S)2
Crystals of the indium iodide adduct 3b were obtained by slow
diffusion of diethyl ether into a dichloromethane solution of the
complex. In order to characterise the binding of the indium to
the platinum–sulfide metalloligand, a single-crystal X-ray diffrac-
tion study was carried out. The structure of the cation is shown
in Fig. 1 together with the atom numbering scheme, while Table
1 gives selected bond lengths and angles.
(PPh3)4InCl3] [4], probably reflecting the cationic, four-coordinate
+
nature of the InI2 fragment in 3b which results in stronger bind-
ing. The dihedral angle between the two PtS2 planes is 126.88°,
There are four molecules of the cation and associated anion,
plus six molecules of dichloromethane of crystallisation in the unit
cell of the primitive, centrosymmetric space group P21/n. The cat-
ion consists of a trimetallic Pt2In core, bridged by two
l3-sulfur
atoms. The In coordination sphere is completed by two iodine
atoms and the platinum centres are each coordinated by two
Fig. 1. Molecular structure of the cation of [Pt2(
ipso carbons of the PPh3 ligands shown for clarity, and thermal ellipsoids at the 50%
l
-S)2(PPh3)4InI2][InI4] 3b with only
Fig. 2. Side view [along the S(1)ꢁ ꢁ ꢁS(2) vector] of the core of [Pt2(l
-S)2(PPh3)4InI2]+
in 3b, showing the symmetric binding of the InI2+ fragment to the metalloligand in
probability level.
the Pt2In plane.

250
W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
which is similar to that in [Pt2(
l
-S)2(PPh3)4InCl3] 2 [128.3(2)°]. The
m/z value (vide infra) when the fragmentation was increased (by
increasing the capillary exit voltage); [Pt2(
-S)2(PPh3)4InCl2]+ was
still observed as part of the overlapping isotopic envelope. Fig. 4
shows selected mass spectra to illustrate the observed species in
(a) a fresh solution of 3c, (b) on standing overnight, and (c) on vary-
ing the fragmentation conditions.
counterion in the structure is [InI4]ꢀ, with a fairly regular tetrahe-
dral geometry; its presence was confirmed by negative-ion ESI MS
analysis, though [InI3Cl]ꢀ and Iꢀ were also observed.
l
The species present in [Pt2(l-S)2(PPh3)4] – indium(III) chloride
reaction mixtures have also been further investigated using posi-
tive-ion ESI MS, a technique only in its infancy at the time of origi-
nal investigations in this area [4]. However, it must be noted that
ESI MS only allows detection of charged species, so a neutral
The dication at m/z 1684 is assigned to the di-indium species
[{Pt2(
mer (formed by fragmentation) is [Pt2(
l
-S)2(PPh3)4InCl(OMe)}2]2+, while its corresponding mono-
l
-S)2(PPh3)4InCl(OMe)]+.
adduct such as [Pt2(
unless some mechanism were operating to provide a charge. The
l
-S)2(PPh3)4InCl3] 2 would not be observed
This is supported by MS measurements; the base peak for the
dication is observed at m/z 1684.644 (calculated m/z 1684.629);
this m/z value is distinctly different from the monocation, which
was observed at m/z 1684.167 (calculated m/z 1684.129). We pro-
most likely pathway is chloride loss, giving [Pt2(l-S)2(PPh3)4
InCl2]+, since other ionisation pathways such as protonation are
inaccessible because of an absence of basic lone pair sites. It was
pose the dication to have a structure with an {In(
(and thus terminal chloride ligands) on the basis that (a) the parent
chloro complex [Pt2(
-S)2(PPh3)4InCl2]+ shows no evidence for for-
l-OMe)2In} unit
previously noted [4] that addition of InCl3 to [Pt2(
InCl3] in CH2Cl2 increased the conductivity around 30-fold, consis-
tent with the formation of an ionic chloride complex [Pt2(
S)2(PPh3)4InCl2][InCl4] analogous to the bromide and iodide
complexes 3a and 3b reported herein. We find that the reaction be-
l-S)2(PPh3)4
l
l
-
mation of a corresponding dicationic dimer in ESI mass spectra,
and (b) there is a demonstrated tendency for alkoxide versus chlo-
ride bridging in indium complexes containing both of these ligands
[27–29], for example [XMeInOR]2 (X = Cl, Br; R = tBu or o-C6H4
OMe) [30]. Such a dimeric species would be expected to undergo
fragmentation to the monomer, as is observed in the mass spectra.
We have seen similar behaviour for the copper-methoxy analogue
tween [Pt2(l-S)2(PPh3)4] and InCl3 in methanol yields a clear, pale
yellow solution which forms a white precipitate on addition of a
large anion (BPh4ꢀ). This complex gave microanalytical data that
match well for [Pt2(l-S)2(PPh3)4InCl2][BPh4] 3c. Complexes 3a, 3b
and 3c all give a single sharp resonance in their 31P{1H} NMR spec-
tra, with virtually identical couplings to 195Pt, ranging from 3172 to
3177 Hz.
[{Pt2(
l , which fragments to [Pt2(l-S)2
-S)2(PPh3)4Cu(OMe)}2]2+
(PPh3)4Cu(OMe)]+ [31].
When a small quantity of pyridine was added to a fresh solution
ESI MS analysis of [Pt2(
l
-S)2(PPh3)4InCl2][BPh4] 3c yielded var-
of 3c in CH2Cl2–MeOH, the dominant species were the methoxy
iable spectra, with the observed ions dependent on the solvent
used, the fragmentation conditions, and the freshness of the
sample solution. When a freshly prepared solution of 3c in MeCN
species [{Pt2(l l-
-S)2(PPh3)4InCl(OMe)}2]2+ and its monomer [Pt2(
S)2(PPh3)4InCl(OMe)]+, with essentially no parent [Pt2(
l-S)2(PPh3)4
InCl2]+ observed, consistent with greater formation of OMeꢀ ions
under the basic conditions. It is noteworthy that the simple five-
solution was analysed, the expected [Pt2(l
-S)2(PPh3)4InCl2]+ was
observed as the base peak in the spectrum (Fig. 3) under a range
of fragmentation conditions. However, analysis in a dichlorometh-
coordinate adduct [Pt2(
served, consistent with previous observations that the [Pt2(
l
-S)2(PPh3)4InCl2(NC5H5)]+ was not ob-
l-
ane-methanol mixture showed, in addition to [Pt2(
InCl2]+ as the base peak, an additional dication at m/z 1684 whose
isotope pattern partly overlaps that of [Pt2(
-S)2(PPh3)4InCl2]+.
When the analyte solution was allowed to stand overnight, the
intensity of the dication increased significantly; under gentle frag-
mentation conditions the dication was the major peak, but frag-
mentation occurred to a monocation at approximately the same
l
-S)2(PPh3)4
S)2(PPh3)4] metalloligand supports the formation of adducts with
low coordination numbers [6,32,33]. A summary of the proposed
solution speciation is given in Scheme 1.
l
The dimer [{Pt2(
the macroscopic scale by reaction of [Pt2(
in methanol in the presence of added trimethylamine base, fol-
l
-S)2(PPh3)4InCl(OMe)}2]2+ was synthesised on
l-S)2(PPh3)4] with InCl3
[{Pt2(µ-S)2(PPh3)4InCl(OMe)}2]2+
[Pt2(µ-S)2(PPh3)4InCl(OMe)]+
m/z 1689.093
m/z 1684
m/z 1684
[Pt2(µ-S)2(PPh3)4InCl2]+
m/z 1688
[Pt2(µ-S)2(PPh3)4InCl2]+
1685
1690
1695
1680
1690
1690
1680
1680
1690
1000
2000
500
1500
m/z
(c)
(b)
(a)
Fig. 3. Positive-ion ESI mass spectrum of [Pt2(
l
-S)2(PPh3)4InCl2][BPh4] 3c in MeCN
solution (Capillary Exit voltage 60 V). The inset shows the expanded isotope pattern
Fig. 4. Positive-ion ESI mass spectra of 3c dissolved in CH2Cl2-MeOH solution: (a)
fresh solution, Capillary Exit 60 V; (b) solution allowed to stand overnight, Capillary
Exit 60 V; (c) solution from (b), Capillary Exit 150 V.
for the dominant cation [Pt2(
theoretical pattern.
l
-S)2(PPh3)4InCl2]+, which agrees well with the

W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
251
Cl
+
Cl
X
X
Cl
In
In
-
S
S
S
2
Y
S
S
S
Pt
Pt
Pt
Pt
Ph P
3
PPh
Ph P
3
PPh
3
Pt
3
Pt
Ph P
3
PPh
3
PPh
Ph P
3
PPh
3
Ph P
3
3
PPh
Ph P
3
3
1
3a, X = Br, Y = [InBr ]
4
3b, X = I, Y = [InI ]
4
3c, X = Cl, Y = BPh
4
2+
Ph P
3
PPh
3
Ph P
PPh
3
3
Pt
Pt
S
S
S
+
Cl
N
In
In
O
2
-
MeO
Cl
OMe
2Y
In
S
-
PF
6
S
Pt
Pt
Ph P
3
PPh
3
S
PPh
Ph P
3
3
Pt
Pt
Ph P
3
PPh
3
PPh
Ph P
3
3
5
4a, Y = BPh
4
4b, Y = PF
6
+
Ph P
3
N
-
Pt
BPh
4
Ph P
3
O
6
S
S
Pt
Pt
Ph P
3
PPh
3
PPh
Ph P
3
3
lnIC3
+
Cl
Cl
Cl
Cl
Cl
In
In
S
S
S
S
Pt
Pt
Pt
Pt
Ph P
3
PPh
Ph P
3
PPh
3
3
PPh
Ph P
3
PPh
3
Ph P
3
3
MeOH
2+
PPh
Ph P
3
3
Ph P
3
PPh
3
Pt
Pt
S
S
+
Cl
OMe
Pt
Cl
In
In
MS fragmentation
S
MeO
Cl
OMe
S
Pt
In
Ph P
3
PPh
3
PPh
Ph P
3
3
S
S
Pt
Pt
Ph P
3
PPh
3
Ph P
3
PPh
3
Scheme 1. The proposed interrelationship between indium-chloride adducts of the metalloligand [Pt2(
l-S)2(PPh3)4].

252
W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
lowed by precipitation of the cation by the addition of excess NaB-
Ph4, giving a white precipitate of [{Pt2( -S)2(PPh3)4InCl(OMe)}2]
(BPh4)2 4a. ESI MS analysis showed [{Pt2( -S)2(PPh3)4InCl(OMe)
}2]2+ to be the dominant ion product, though some [Pt2(
-S)2
(PPh3)4InCl2]+ was observed. The 31P{1H} NMR spectrum of 4a
showed
single central resonance with 195Pt coupling of
3124 Hz, slightly less than in the four-coordinate dichloro complex
3c (3172 Hz); this can be rationalised by the fact that in 4a the in-
dium is five-coordinate and therefore probably less Lewis acidic
than in 3c, resulting in the (more electron-rich) sulfide ligands of
4a exerting a slightly higher trans-influence, decreasing 1J(PtP) to
the trans phosphine.
yellow tetraphenylborate salt 6, which displays a dull red lumines-
cence when irradiated at either 254 or 312 nm. The complex is
soluble in chlorinated hydrocarbon solvents and gives the expected
cation as the sole peak in the positive-ion ESI mass spectrum at m/z
863.214 (calcd. 863.192). The X-ray structure of 6 was determined,
and the cation together with the atom numbering scheme are
shown in Fig. 5.
In 6, the Pt–O bond distance [2.0356(17) Å] is slightly longer
than in the complex PtQ2 [44], 2.014(3) Å. The Pt–N distance of 6
[2.115(2) Å] is also significantly longer than the Pt–N distance of
PtQ2 [1.993(4) Å]. These increased bond lengths in 6 reflect the
relatively high trans-influence [45] of the phosphine ligands, which
cause of lengthening of the trans Pt–ligand bonds. A similar length-
ening was observed for the Pt–O bond of a platinum Q complex
containing a cyclometallated phenylpyridine ligand (with the Pt–
l
l
l
a
Unfortunately, attempts at obtaining single crystals of 4a suit-
able for an X-ray structural study have been unsuccessful; vapour
diffusion of diethyl ether into a dichloromethane solution of the
complex gave colourless, finely acicular crystals. The correspond-
O bond trans to the strong trans-influence
r-phenyl ligand) [39].
ing hexafluorophosphate salt [{Pt2(
l
-S)2(PPh3)4InCl(OMe)}2](PF6)2
The Pt–P(1) bond trans to oxygen O(1) is slightly longer
[2.2626(7) Å] compared to Pt–P(2) trans to quinoline nitrogen
[2.2578(7) Å], reflecting a slightly higher trans-influence for the an-
ionic oxygen donor. The bite angle of the ligand [O(1)–Pt(1)–N(1)]
is 80.53(8)°, somewhat reduced from the idealised bond angle of
90° at platinum(II), with a concomitant widening of the P(1)–
Pt(1)–P(2) angle to 96.14(3)°. As a result of the geometry of the
Q ligand, the bond angle N(1)–Pt(1)–P(1) [95.58(6)°] is wider than
on the other side of the complex [O(1)–Pt(1)–P(2) 87.64(5)°]. As is
common in platinum(II) complexes, the metal is slightly distorted
from an idealised square-planar geometry, with an angle of
6.27(6)° between the P(1)–Pt(1)–P(2) and O(1)–Pt(1)–N(1) planes;
the platinum–oxyquinolinate system is, however, highly planar.
4b was also synthesised in high purity (as shown by ESI MS and
microelemental analysis) but also yielded no crystals suitable for
X-ray crystallographic study.
2.2. Chemistry of [Pt2(l-S)2(PPh3)4] with indium(III) complexes of
bidentate chelating ligands
Reaction of a methanolic suspension of [Pt2(l-S)2(PPh3)4] with
InCl3ꢁ3H2O, 2 mole equivalents of 8-hydroxyquinoline (HQ) and
excess trimethylamine base gave a bright yellow solution from
which the salt [Pt2(l-S)2(PPh3)4InQ2]PF6 5 was isolated in 70%
yield as a yellow solid by addition of excess ammonium hexa-
fluorophosphate. The complex is soluble in chloroform and dichlo-
romethane. The 31P{1H} NMR spectrum of the complex in CDCl3
showed two well-resolved singlet resonances at d 21.5 and 16.4,
showing coupling to 195Pt of 3175 and 3069 Hz, respectively. These
arise due to two inequivalent sets of PPh3 ligands that arise
because of the N/O asymmetry of the Q ligand. The ESI mass spec-
trum shows a single ion at m/z 1906.323 which shows excellent
agreement of its isotope pattern and m/z value with theoretical val-
ues. In contrast to the bright yellow luminescence displayed by
Attempts at the synthesis of related indium adducts of [Pt2(l-
S)2(PPh3)4] with other ancillary chelating ligands on indium have
met with partial success, with some mixed-ligand complexes also
being formed by the method used to prepare 5. Thus, reaction of
[Pt2(
l
-S)2(PPh3)4] with 1 mole equivalents of InCl3ꢁ3H2O and
2 mole equivalents of the dithiocarbamate NH4[S2CN(CH2)4],
followed by precipitation of the cationic products with NH4PF6
InQ3 [34–36] [Pt2(l-S)2(PPh3)4InQ2]PF6 displayed only an extre-
mely faint yellow luminescence when irradiated at either 254 or
312 nm. Like InQ3, complex 5 is proposed to also contain six
-coordinate indium, though we were unable to obtain single crys-
tals suitable for an X-ray study. When [Pt2(l-S)2(PPh3)4] was
reacted with 1 mole equivalent of each of InCl3ꢁ3H2O and
8-hydroxyquinoline in an attempt to synthesise the mono-chloro
complex [Pt2(
tained, which was found by ESI MS to be a mixture of all three
l
-S)2(PPh3)4InClQ]+, a light yellow solid was ob-
+
Cl/Q complexes [Pt2(
The reaction of [Pt2(
smoothly; reaction in methanol suspension gives a yellow suspen-
sion found to contain [Pt2(
-S)2(PPh3)4InQ2]+, but contaminated
l-S)2(PPh3)4InClnQ2ꢀn] (n = 0–2).
l-S)2(PPh3)4] with InQ3 itself proceeds less
l
with a species at m/z 863, identified as the platinum(II) species
[(Ph3P)2PtQ]+. The formation of [(Ph3P)2PtQ]+ presumably arises
from attack of the librated Qꢀ anion on the initially-formed
[Pt2(
Similar behaviour has been observed before in reactions of
[Pt2( -S)2(PPh3)4] with diketonate complexes of cobalt(II) and zin-
l
-S)2(PPh3)4InQ2]+, resulting in breakup of the {Pt2S2} core.
l
c(II), where the liberated diketonate anion leads to mononuclear
complexes [(Ph3P)2Pt(diketonate)]+ [37].
Examination of the literature indicated that while a substantial
number of platinum complexes containing chelating hydroxyquin-
olinate ligands have been reported [38–43], complexes containing
ancillary phosphine ligands are surprisingly unknown. [(Ph3P)2
PtQ]+ was readily prepared by reaction of cis-[PtCl2(PPh3)2] with
excess HQ in hot methanol, in the presence of trimethylamine
base. The resulting cation was isolated in good yield as its bright
Fig. 5. Structure of the cation of [PtQ(PPh3)2]BPh4 6 showing the atom numbering
scheme. Thermal ellipsoids are shown at the 50% probability level. Selected bond
lengths (Å) and angles (°): Pt(1)–O(1) 2.0356(17), Pt(1)–N(1) 2.115(2), Pt(1)–P(2)
2.2578(7), Pt(1)–P(1) 2.2626(7), O(1)–C(2) 1.324(3), N(1)–C(9) 1.326(3), N(1)–C(1)
1.386(3), O(1)–Pt(1)–N(1) 80.53(8), O(1)–Pt(1)–P(2) 87.64(5), N(1)–Pt(1)–P(1)
95.58(6), P(2)–Pt(1)–P(1) 96.14(3).

W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
253
gave a light yellow solid found by ESI MS to contain predominantly
[Pt2(
-S)2(PPh3)4In{S2CN(CH2)4}2]+ (m/z 1910) but contaminated
with around 25% [Pt2(
-S)2(PPh3)4InCl{S2CN(CH2)4}]+ (m/z 1799).
diethyl ether into a dichloromethane solution of the complex gave
colourless crystals.
l
l
When this reaction is repeated but using 2 mole equivalents of
Na(S2CNEt2) as the dithiocarbamate ligand, and the product pre-
cipitated using NaBPh4, analogous cationic species were formed,
3.2. Synthesis of [Pt2(l-S)2(PPh3)4InI2][InI4] 3b
Following the procedure for the InBr2 adduct 3a, but replacing
NaBr with KI, [Pt2( -S)2(PPh3)4] (273 mg, 0.182 mmol) gave a
cream precipitate of [Pt2( -S)2(PPh3)4InI2][InI4] 3b (337 mg, 74%).
72H60I6In2P4Pt2S2 (Mr 2493.5) requires C, 34.65; H, 2.42; N, 0.00.
Found: C, 34.80; H, 2.46; N, 0.00%. Positive-ion ESI MS (MeOH sol-
but with the chloro complex [Pt2(
(m/z 1801) the major species, and [Pt2(
l
l
-S)2(PPh3)4InCl(S2CNEt2)]+
l
-S)2(PPh3)4In(S2CNEt2)2]+
l
(m/z 1914) at about 30% relative intensity. No further studies were
carried out on these systems.
C
In summary, we have extended the range of known indium(III)
vent): [Pt2(l
-S)2(PPh3)4InI2]+ (m/z 1870.963, calcd. 1870.950).
adducts of the metalloligand [Pt2(l-S)2(PPh3)4] to include four-
Negative-ion ESI MS (MeOH): Iꢀ (m/z 126.886), [InI3Cl]ꢀ (m/z
530.533), [InI4]ꢀ (m/z 622.463). 31P{1H} NMR, d 17.0 [s, 1J(PtP)
3175]. Recrystallisation by vapour diffusion of diethyl ether into
a dichloromethane solution of the complex gave very pale cream
crystals suitable for a single-crystal X-ray study.
coordinate chloro-, bromo- and iodo-complexes, with partial
methanolysis being observed for solely the chloro system. ESI MS
has again found to be a useful methodology for probing the chem-
istry of this system, and we are continuing our investigations into
hydroxyquinolinate adducts with other metals.
3.3. Synthesis of [Pt2(l-S)2(PPh3)4InCl2][BPh4] 3c
A suspension of [Pt2(l-S)2(PPh3)4] (300 mg, 0.200 mmol) and
3. Experimental
InCl3ꢁ3H2O (57 mg, 0.207 mmol) in methanol (30 mL) was stirred
at room temp. for 1.5 h, giving a clear, very pale yellow solution.
Solid NaBPh4 (200 mg, 0.585 mmol) was added to the stirred solu-
tion, immediately forming a white precipitate. The product was
filtered, washed with cold methanol (2 ꢂ 3 mL) and dried under
[Pt2(l-S)2(PPh3)4] [46,47] and InQ3 [48] were prepared by the
literature procedures. Ammonium hexafluorophosphate (Aldrich),
sodium tetraphenylborate (BDH), indium trichloride trihydrate
(BDH), indium nitrate hydrate (BDH), sodium bromide (BDH),
potassium iodide (BDH), aqueous trimethylamine solution
(25–30% w/v, BDH), ammonium pyrollidinedithiocarbamate
(NH4[S2CN(CH2)4], BDH), sodium diethyldithiocarbamate (BDH)
and 8-hydroxyquinoline (Riedel de Haën) were used as supplied
from commercial sources.
vacuum to give 3c as
a
white solid (310 mg, 77%).
C
96H80BCl2InP4Pt2S2 (Mr 2007.4) requires C, 57.39; H, 4.02; N,
0.00. Found: C, 56.73; H, 3.88; N, 0.00%. Positive-ion ESI MS (MeCN)
[Pt2(
-S)2(PPh3)4InCl2]+ (m/z 1689.093, calcd. 1689.079); refer also
Section 2. 31P{1H} NMR, d 17.27 [s, 1J(PtP) 3172].
l
Low resolution ESI mass spectra were recorded on a VG Plat-
form II instrument. High resolution ESI mass spectra were recorded
on a Bruker MicrOTOF instrument, which was periodically cali-
brated using a solution of sodium formate. Samples of isolated
products were typically prepared for analysis by dissolution in a
few drops of dichloromethane followed by dilution with methanol
and centrifugation. Typical parameters used a Capillary Exit voltage
of 150 V though this was varied in increments between 60 and
180 V to investigate variable fragmentation conditions on ion
speciation. Assignment of ions was assisted by comparison of
experimental and theoretical isotope patterns, the latter calculated
using an internet-based program [49] or instrument-based
software.
3.4. Synthesis of [{Pt2(
l
-S)2(PPh3)4InCl(OMe)}2](BPh4)2 4a
To a suspension of [Pt2(
l
-S)2(PPh3)4] (298 mg, 0.198 mmol) in
methanol (30 mL) was added InCl3ꢁ3H2O (80 mg, 0.29 mmol) and
the mixture stirred for 30 min to give a clear, very pale yellow solu-
tion. Aqueous trimethylamine solution (10 drops) was added,
resulting in some precipitate formation. Dichloromethane (ca.
3 mL) was then added, and the mixture gravity filtered. To the
resulting clear pale yellow filtrate was added NaBPh4 (300 mg,
0.877 mmol), giving a white precipitate. The product was filtered,
washed with cold methanol (5 mL) and dried under vacuum to give
4a (214 mg, 54%). C194H166B2Cl2In2O2P8Pt4S4 requires C, 58.12; H,
4.18. Found: C, 56.94; H, 4.29%. Positive ion ESI MS (CH2Cl2–MeOH)
31P{1H} NMR spectra were recorded in CDCl3 solution on a Bru-
ker DRX instrument at 162 MHz. Elemental analyses were carried
out by the Campbell Microanalytical Laboratory, University of
Otago, Dunedin, New Zealand. Reactions were carried out in LR
grade methanol solvent without regard for the exclusion of light,
air, or moisture.
[{Pt2(
l
-S)2(PPh3)4InCl(OMe)}2]2+ (m/z 1684.167, calcd. 1684.129).
31P{1H} NMR, d 17.6 [s, 1J(PtP) 3124].
3.5. Synthesis of [{Pt2(l-S)2(PPh3)4InCl(OMe)}2](PF6)2 4b
Following the general procedure for the synthesis of 4a, com-
plex 4b was prepared in 49% yield, from [Pt2( -S)2(PPh3)4]
l
3.1. Synthesis of [Pt2(
l
-S)2(PPh3)4InBr2][InBr4] 3a
-S)2(PPh3)4] (333 mg, 0.222 mmol) in
(242 mg, 0.161 mmol) with NH4PF6 (300 mg) as the precipitating
agent; water (10 mL) was added to assist precipitation. Positive
ion ESI MS (CH2Cl2–MeOH) showed the product to contain pure
To a suspension of [Pt2(
l
methanol (20 mL) was added an excess (300 mg) of In(NO3)3ꢁxH2O,
rapidly giving a clear pale yellow solution. After stirring for 5 min a
large excess (2.5 g) of sodium bromide was added, giving a white
flocculent precipitate that was stirred for 5 min and then water
(60 mL) added. After stirring for 20 min the white product was fil-
tered, washed with water (2 ꢂ 10 mL) and dried under vacuum to
give 3a (298 mg, 61%). C72H60Br6In2P4Pt2S2 (Mr 2211.6) requires C,
39.07; H, 2.73; N, 0.00. Found: C, 38.83; H, 2.77; N, 0.00%. Positive-
[{Pt2(l
-S)2(PPh3)4InCl(OMe)}2]2+ with no other Pt–In species. C146
H126Cl2F12In2O2P10Pt4S4 requires C, 47.90; H, 3.47. Found: C,
47.50; H, 3.36%.
3.6. Synthesis of [Pt2(l-S)2(PPh3)4InQ2]PF6
5
A suspension of [Pt2(l-S)2(PPh3)4] (344 mg, 0.229 mmol) and
InCl3ꢁ3H2O (65 mg, 0.236 mmol) in methanol (30 mL) was stirred
at room temp. for 20 min giving a clear, very pale yellow solution.
To this was added 8-hydroxyquinoline (HQ; 67 mg, 0.462 mmol)
giving a slightly more yellow solution, followed by aqueous tri-
methylamine (1 mL, excess). After stirring for 40 min the yellow
ion ESI MS (MeOH solvent): [Pt2(l
-S)2(PPh3)4InBr2]+ (m/z
1777.988, calcd. 1777.977) together with a trace of [Pt2(l-S)2
(PPh3)4InBrCl]+ (m/z 1733.036, calcd. 1733.028). 31P{1H} NMR, d
16.9 [s, 1J(PtP) 3177]. Recrystallisation by vapour diffusion of

254
W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
solution was filtered to remove a trace of insoluble matter, and
NH4PF6 (200 mg, 1.23 mmol) added to the filtrate, giving a yellow
precipitate. Water (10 mL) was added to assist precipitation, and
the product was isolated by filtration, washed with methanol–
water (1:1, 10 mL) and dried under vacuum to give 5 (330 mg,
70%). C90H72F6InN2O2P5Pt2S2 (Mr 2050.3) requires C, 52.67; H,
3.54; N, 1.37. Found: C, 51.88; H, 3.46; N, 1.33%. Positive-ion ESI
3.10. X-ray structure determination on [Pt2(l-S)2(PPh3)4InI2][InI4] 3b
Crystals were obtained from dichloromethane–diethyl ether.
Crystal data for C73.50H63Cl3I6In2P4Pt2S2; Mr = 2621.81; mono-
clinic; space group P21/n; a = 17.472(2) Å; b = 22.264(3) Å;
c = 21.028(2) Å; b = 93.744(2)°; V = 8162.5(16) Å3; Z = 4; T = 120
(2) K; k(Mo K
2.133 g cmꢀ3
(Rint = 0.0513); giving R1 = 0.0278, wR2 = 0.0516 for 13 604 data
a
) = 0.71073 Å;
l
(Mo K
a
) = 6.511 mmꢀ1
;
dcalc =
MS m/z 1906.323 (100%); calcd. for [Pt2(
l
-S)2(PPh3)4InQ2]+ m/z
d
21.5 [s, 1J(PtP) 3175] and 16.4
;
98 992 reflections collected; 16 736 unique
1906.233. 31P{1H} NMR,
[s, 1J(PtP) 3069].
with [I > 2r(I)] and R1 = 0.0413, wR2 = 0.0566 for all 16 736 data.
Residual electron density (e– Åꢀ3) max/min: 1.547/ꢀ1.421.
An arbitrary sphere of data were collected on a tablet-like crys-
tal, having approximate dimensions of 0.32 ꢂ 0.19 ꢂ 0.09 mm, on a
3.7. Attempted synthesis of [Pt2(l-S)2(PPh3)4InClQ]PF6
A suspension of [Pt2( -S)2(PPh3)4] (221 mg, 0.147 mmol) and
l
Bruker Kappa X8-APEX-II diffractometer using a combination of x-
InCl3ꢁ3H2O (41 mg, 0.149 mmol) in methanol (30 mL) was stirred
at room temp. for 5 min giving a clear, very pale yellow solution.
8-Hydroxyquinoline (22 mg, 0.152 mmol) was added, followed
after 5 min by four drops of aqueous Me3N solution, giving a light
yellow solution. After stirring (with no further change) for 1.5 h,
the solution was filtered to remove a trace of insoluble material,
and NH4PF6 (200 mg, 1.23 mmol) added to the filtrate, giving a
light lemon-yellow precipitate. The solid was filtered, washed with
cold methanol (5 mL) and dried under vacuum to give 198 mg of a
light yellow solid. Positive-ion ESI MS showed major ions due to
and u-scans of 0.3°. Data were corrected for absorption and polar-
isation effects and analysed for space group determination. The
structure was solved by direct methods and expanded routinely.
The model was refined by full-matrix least-squares analysis of F2
against all reflections. All non-hydrogen atoms were refined with
anisotropic thermal displacement parameters. Unless otherwise
noted, hydrogen atoms were included in calculated positions.
Thermal parameters for the hydrogens were tied to the isotropic
thermal parameter of the atom to which they are bonded (1.2 ꢂ for
all C–H).
Three locations for solvent molecules (modelled as dichloro-
methane) were observed in the asymmetric unit. Two sites are
near each other and represent a full molecule of solvent disordered
over two sites, the third site is located on a centre of symmetry. Ini-
tially all site occupancies were refined independently leading to
occupancies of 0.71, 0.29 and 0.51. Subsequently the two close
sites (which initially refined to 0.71 and 0.29 occupancy) were then
refined with occupancies summed to unity. The remaining site was
refined with an occupancy fixed at 0.5. The thermal parameter of
the minor component solvent carbon atom was refined isotropi-
cally, all other non-hydrogen atoms were refined with anisotropic
thermal parameters.
[Pt2(
l
-S)2(PPh3)4InQ2]+ (m/z 1906), [Pt2(
l
-S)2(PPh3)4InClQ]+
(m/z 1797) and [Pt2(
l
-S)2(PPh3)4InCl2]+ (m/z 1689).
3.8. Synthesis of [Pt2(l-S)2(PPh3)4In{S2CN(CH2)4}2]PF6
A mixture of [Pt2(l-S)2(PPh3)4] (360 mg, 0.240 mmol) and
InCl3ꢁ3H2O (68 mg, 0.248 mmol) in methanol (25 mL) was stirred
at room temp. for 10 min giving a clear, very pale yellow solution.
NH4[S2CN(CH2)4] (81 mg, 0.493 mmol) was added and the mixture
stirred for 10 min giving a light yellow solution. After filtration to
remove a trace of insoluble material, NH4PF6 (200 mg, 1.23 mmol)
was added giving a light yellow precipitate. The product was iso-
lated by filtration, washed with water (5 mL) and dried under vac-
uum to give 349 mg of product as a yellow powder. Positive-ion ESI
3.11. X-ray structure determination on [PtQ(PPh3)2]BPh4
6
MS of the product showed predominantly [Pt2(l-S)2(PPh3)4
In{S2CN(CH2)4}2]+ at m/z 1910.164 (relative intensity 100%, calcd
m/z 1910.162) together with around 25% relative intensity of the
Crystals were obtained from dichloromethane–diethyl ether.
Crystal data for C75H62BNOP2Pt; Mr = 1261.10; Triclinic; space
-S)2(PPh3)4InCl{S2CN(CH2)4}]+ at m/z
group P1; a = 12.5329(18) Å; b = 14.574(2) Å; c = 19.111(3) Å;
ꢀ
chloro-derivative [Pt2(
l
1799.124 (calcd. 1799.121).
a = 68.500(2)°; b = 88.726(2)°; c
= 65.029(2)°; V = 2907.6(7) Å3;
When the above reaction was repeated using [Pt2(
l
-S)2(PPh3)4]
Z = 2; T = 120(2) K; k(Mo K
a
) = 0.71073 Å;
l(Mo Ka) = 2.516
(369 mg, 0.246 mmol), InCl3ꢁ3H2O (68 mg, 0.248 mmol), Na(S2C-
NEt2) (85 mg, 0.497 mmol) and NaBPh4 (200 mg, 0.585 mmol),
374 mg of a light yellow solid was obtained that was found to be
mmꢀ1; dcalc = 1.440 g cmꢀ3; 39 711 reflections collected; 11 849
unique (Rint = 0.0343); giving R1 = 0.0240, wR2 = 0.0489 for 10 784
data with [I > 2r(I)] and R1 = 0.0285, wR2 = 0.0538 for all 11 849
a mixture of [Pt2(
1801.131, calcd. 1801.136) and [Pt2(
(minor product, m/z 1914.186, calcd. 1914.193).
l
-S)2(PPh3)4InCl(S2CNEt2)]+ (major product, m/z
data. Residual electron density (e– Åꢀ3) max/min: 0.912/ꢀ0.564.
l
-S)2(PPh3)4In(S2CNEt2)2]+
An arbitrary sphere of data were collected on a pale yellow
block-like
0.23 ꢂ 0.15 ꢂ 0.14 mm, on a Bruker APEX-II diffractometer using
a combination of - and -scans of 0.3°. Data were corrected for
crystal,
having
approximate
dimensions
of
3.9. Synthesis of [PtQ(PPh3)2]BPh4
6
x
u
absorption and polarisation effects and analysed for space group
determination. The structure was solved by direct methods and
expanded routinely. The model was refined by full-matrix least-
squares analysis of F2 against all reflections. All non-hydrogen
atoms were refined with anisotropic thermal displacement param-
eters. Unless otherwise noted, hydrogen atoms were included in
calculated positions. Thermal parameters for the hydrogens were
tied to the isotropic thermal parameter of the atom to which they
are bonded (1.2ꢂ for all others).
A suspension of cis-[PtCl2(PPh3)2] (225 mg, 0.285 mmol) and
8-hydroxyquinoline (200 mg, 1.38 mmol) in methanol (30 mL)
with aqueous trimethylamine (1 mL, excess) was heated to reflux
for 20 min to give a clear, bright yellow solution. After filtration
to remove
a trace of insoluble material, NaBPh4 (250 mg,
0.73 mmol) was added to the warm filtrate, giving a bright yellow
precipitate. This was isolated by filtration, washed with cold meth-
anol (2 ꢂ 5 mL) and dried under vacuum to give 6 (296 mg, 88%).
C69H56BNOP2Pt (Mr 1182.5) requires C, 70.02; H, 4.77; N, 1.18.
Found: C, 70.15; H, 4.83; N, 1.15%. Positive-ion ESI MS m/z
863.214 (100%); calcd, for [Pt(PPh3)2Q]+ m/z 863.192. 31P{1H}
NMR (CDCl3), d 14.1 [d, 1J(PtP) 3680, 2J(PP) 19] and 8.7 [d, 1J(PtP)
3396, 2J(PP) 19].
Acknowledgements
We thank the Universities of Waikato and Notre Dame for
financial support of this work. We also thank Julia Lin and Antony

W. Henderson, A.G. Oliver / Inorganica Chimica Acta 375 (2011) 248–255
255
[20] A.A. Shvartsburg, J. Am. Chem. Soc. 124 (2002) 12343.
[21] J. Chan, A.L. Thompson, M.W. Jones, J.M. Peach, Inorg. Chim. Acta 363 (2010)
1140.
Parnell for recording the NMR spectra and James Bridson for the
sample of InQ3 and some preliminary experiments.
[22] D.E. Green, C.L. Ferreira, R.V. Stick, B.O. Patrick, M.J. Adam, C. Orvig, Bioconjug.
Chem. 16 (2005) 1597.
[23] K. Mohammadi, K.H. Thompson, B.O. Patrick, T. Storr, C. Martins, E. Polishchuk,
V.G. Yuen, J.H. McNeill, C. Orvig, J. Inorg. Biochem. 99 (2005)
2217.
[24] A.C. Stenson, E.A. Cioffi, Rapid Commun. Mass Spectrom. 21 (2007)
2594.
[25] S.-W.A. Fong, K. Evans, W. Henderson, B.K. Nicholson, T.S.A. Hor, Inorg. Chim.
Acta 363 (2010) 301.
[26] G.L. Abbati, M.C. Aragoni, M. Arca, F.A. Devillanova, A.C. Fabretti, A. Garau, F.
Isaia, V. Lippolis, G. Verani, Dalton Trans. (2003) 1515.
[27] K. Saatchi, B.O. Patrick, C. Orvig, Dalton Trans. (2005) 2268.
[28] A. Pietrangelo, S.C. Knight, A.K. Gupta, L.J. Yao, M.A. Hillmyer, W.B. Tolman, J.
Am. Chem. Soc. 132 (2010) 11649.
[29] R.W. Saalfrank, C. Deutscher, H. Maid, A.M. Ako, S. Sperner, T. Nakajima, W.
Bauer, F. Hampel, B.A. Hess, N.J.R. van Eikema Hommes, R. Puchta, F.W.
Heinemann, Chem. Eur. J. 10 (2004) 1899.
[30] M. Veith, S. Hill, V. Huch, Eur. J. Inorg. Chem. (1999) 1343.
[31] S.M. Devoy, W. Henderson, B.K. Nicholson, J. Fawcett, T.S.A. Hor, Dalton (2005)
2780.
[32] W. Henderson, T.S.A. Hor, Inorg. Chim. Acta 363 (2010) 1859.
[33] S.-W.A. Fong, T.S.A. Hor, W. Henderson, B.K. Nicholson, S. Gardyne, S.M. Devoy,
J. Organomet. Chem. 679 (2003) 24.
[34] I. Hernández, W.P. Gillin, J. Phys. Chem. B 113 (2009) 14079.
[35] I. Hernández, W.P. Gillin, M. Somerton, J. Lumin. 129 (2005) 1835.
[36] B.J. Chen, X.W. Sun, Y.K. Li, Appl. Phys. Lett. 82 (2003) 3017.
[37] J.H. Bridson, W. Henderson, B.K. Nicholson, T.S.A. Hor, Inorg. Chim. Acta 359
(2006) 680.
[38] F. Niedermair, O. Kwon, K. Zojer, S. Kappaun, G. Trimmel, K. Mereiter, C.
Slugovc, Dalton Trans. (2008) 4006.
[39] N.M. Shavaleev, H. Adams, J. Best, R. Edge, S. Navaratnam, J.A. Weinstein, Inorg.
Chem. 45 (2006) 9410.
[40] X.-N. Li, J.-K. Feng, A.-M. Ren, L.-J. Li, Synth. Met. 157 (2007) 1046.
[41] H. Hoshino, M. Suzuki, M. Kan’no, T. Ohmachi, T. Yotsuyanagi, Anal. Chim. Acta
407 (2000) 71.
[42] D. Donges, J.K. Nagle, H. Yersin, Inorg. Chem. 36 (1997) 3040.
[43] R. Ballardini, M.T. Indelli, G. Varani, C.A. Bignozzi, F. Scandola, Inorg. Chim. Acta
31 (1978) L423.
[44] M. Kato, Y. Ogawa, M. Kozakai, Y. Sugimoto, Acta Crystallogr., Sect. C 58 (2002)
m147.
[45] T.G. Appleton, H.C. Clark, L.E. Manzer, Coord. Chem. Rev. 10 (1973) 335.
[46] W. Henderson, S. Thwaite, B.K. Nicholson, T.S.A. Hor, Eur. J. Inorg. Chem. (2008)
5119.
Appendix A. Supplementary material
CCDC 812347 and 812346 contain the supplementary crystallo-
graphic data for (3b) and (6). These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
http://www.ccdc.cam.ac.uk/data_request/cif. Supplementary data
associated with this article can be found, in the online version, at
doi:10.1016/j.ica.2011.05.014.
References
[1] S.-W.A. Fong, T.S.A. Hor, J. Chem. Soc., Dalton Trans. (1999) 639.
[2] P. González-Duarte, A. Lledós, R. Mas-Ballesté, Eur. J. Inorg. Chem. (2004) 3585.
[3] A.L. Tan, M.L. Chiew, T.S.A. Hor, J. Mol. Struct. (Theochem.) 393 (1997) 189.
[4] M. Zhou, Y. Xu, C.-F. Lam, P.-H. Leung, L.-L. Koh, K.F. Mok, T.S.A. Hor, Inorg.
Chem. 33 (1994) 1572.
[5] M. Zhou, Y. Xu, A.-M. Tan, P.-H. Leung, K.F. Mok, L.-L. Koh, T.S.A. Hor, Inorg.
Chem. 34 (1995) 6425.
[6] M. Zhou, Y. Xu, L.-L. Koh, K.F. Mok, P.-H. Leung, T.S.A. Hor, Inorg. Chem. 32
(1993) 1875.
[7] S.L. Rose, W. Henderson, B.K. Nicholson, T.S.A. Hor, Inorg. Chim. Acta 362
(2009) 5237.
[8] J.S.L. Yeo, J.J. Vittal, W. Henderson, T.S.A. Hor, J. Chem. Soc., Dalton Trans.
(2002) 328.
[9] G. Li, C.-K. Lam, S.W. Chien, T.C.W. Mak, T.S.A. Hor, J. Organomet. Chem. 690
(2005) 990.
[10] T. Todorov, E. Cordoncillo, J.F. Sanchez-Royo, J. Carda, P. Escribano, Chem.
Mater. 18 (2006) 3145.
[11] J.-J. Wang, F.-F. Cao, L. Jiang, Y.-G. Guo, W.-P. Hu, L.-J. Wan, J. Am. Chem. Soc.
131 (2009) 15602.
[12] K. Nose, T. Omata, S. Otsuka-Yao-Matsuo, J. Phys. Chem. C 113 (2009) 3455.
[13] W. Han, L. Yi, N. Zhao, A. Tang, M. Guo, Z. Tang, J. Am. Chem. Soc. 130 (2008)
13152.
[14] J.S.L. Yeo, J.J. Vittal, W. Henderson, T.S.A. Hor, J. Organomet. Chem. 659 (2002)
92.
[15] A.J. Canty, R. Colton, I.M. Thomas, J. Organomet. Chem. 455 (1993) 283.
[16] A.N. Kuznetsov, B.A. Popovkin, W. Henderson, M.J. Taylor, L. Bengtsson-Kloo, J.
Chem. Soc., Dalton Trans. (2000) 1777.
[17] K. Koszinowski, J. Am. Chem. Soc. 132 (2010) 6032.
[18] W. Henderson, M.J. Taylor, Inorg. Chim. Acta 277 (1998) 26.
[19] E. Vasca, D. Ferri, C. Manfredi, L. Torello, C. Fontanella, T. Caruso, S. Orrù, Dalton
Trans. (2003) 2698.
[47] R. Ugo, G. La Monica, S. Cenini, A. Segre, F. Conti, J. Chem. Soc. (1971) 522.
[48] J. Wang, K.D. Oyler, S. Bernhard, Inorg. Chem. 46 (2007) 5700.
[49] <http://fluorine.ch.man.ac.uk/research/mstool.php>.