Dehydrogenative stannane coupling by platinum complexes

Article abstract of DOI:10.1016/S0020-1693(02)01539-6

The complexes Pt(acac)₂, (PhMe₂P) ₂PtMe₂, (dppe)PtMe₂ (dppe=bis(diphenylphosphino)ethane) , and the (P∩N)PtMe₂ complexes [(κ²-P,N)-Ph ₂PCH₂CH₂CH₂NMe₂]PtMe ₂ and [(κ²-P,N)-Ph₂PCH₂CH ₂NMe₂]PtMe₂ catalyse the formation of distannanes by dehydrogenative coupling of triphenyltin hydride or tri-n-butyltin hydride. While Pt(acac)₂ appears to react by a radical mechanism, the bis(stannyl) complexes (PhMe₂P) ₂Pt(SnR₃)₂ and (dppe)Pt(SnR₃) ₂ were observed in the reaction of (PhMe₂P) ₂PtMe₂ and (dppe)PtMe₂. At longer reaction periods the complexes (PhMe₂P)₂Pt(H)SnBu₃ and (PhMe₂P)₂Pt(Ph)SnHPh₂, respectively, were formed. There is evidence that the distannanes are formed by a similar mechanism when (P∩N)PtMe₂ is employed as the catalyst instead of (R₃P)₂PtMe₂. However, the presence of the P,N-chelating ligand results in the stabilisation of the intermediate (P∩N)Pt(Me)SnR₃ and in the formation of redistribution products.

Full text of DOI:10.1016/S0020-1693(02)01539-6

Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
www.elsevier.com/locate/ica
Dehydrogenative stannane coupling by platinum complexes
Susan M. Thompson, Ulrich Schubert *
Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/165, A-1060 Vienna, Austria
Received 28 June 2002; accepted 14 October 2002
In honor of Professor Pierre Braunstein
Abstract
The complexes Pt(acac)2, (PhMe2P)2PtMe2, (dppe)PtMe2 (dppeꢀ
/
bis(diphenylphosphino)ethane), and the (PS N)PtMe2
/
complexes [(k2-P,N)ÃPh2PCH2CH2CH2NMe2]PtMe2 and [(k2-P,N)Ã
/
/
Ph2PCH2CH2NMe2]PtMe2 catalyse the formation of di-
stannanes by dehydrogenative coupling of triphenyltin hydride or tri-n-butyltin hydride. While Pt(acac)2 appears to react by a
radical mechanism, the bis(stannyl) complexes (PhMe2P)2Pt(SnR3)2 and (dppe)Pt(SnR3)2 were observed in the reaction of
(PhMe2P)2PtMe2 and (dppe)PtMe2. At longer reaction periods the complexes (PhMe2P)2Pt(H)SnBu3 and (PhMe2P)2Pt(Ph)SnHPh2,
respectively, were formed. There is evidence that the distannanes are formed by a similar mechanism when (PS
employed as the catalyst instead of (R3P)2PtMe2. However, the presence of the P,N-chelating ligand results in the stabilisation of the
intermediate (PS N)Pt(Me)SnR3 and in the formation of redistribution products.
/N)PtMe2 is
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Platinum complexes; Stannyl complexes; Homogeneous catalysts; Hemilabile ligands
1. Introduction
reaction when hemilabile ligands are used in reactions of
Group IV compounds.
The formation of SnÃ
coupling is much more favourable than the formation of
SiÃSi bonds due to the weaker HÃSn bond (252 kJ
molꢁ1) compared with the HÃSi bond (323 kJ molꢁ1
[3]. Organotin hydrides HSnR3 are known to undergo
dehydrogenative dimerization with various types of
catalyst, e.g. amines or transition metal catalysts such
as (Ph3P)2PdCl2 or Pd(Ph3P)4 [4]. Whether these reac-
tions proceed or not depends strongly on the substitu-
ents at the tin atom. Dehydrogenative stannane
dimerizations do not normally proceed at ambient
temperatures or spontaneously. For example, using
AIBN as a catalyst to form Sn2Ph6 from HSnPh3
requires temperatures of over 100 8C [5].
The reactivity of platinum complexes towards silanes
is greatly enhanced when hemilabile chelating P,N
ligands are employed as opposed to the more common
bis-phosphine complexes [1]. While an interesting vari-
ety of catalytic and stoichiometric reactions were found
/
Sn bonds by dehydrogenative
/
/
/
)
in which siliconÃ
formed from hydrogenosilanes and chlorosilanes, dehy-
drogenative silane coupling was conspicuously absent.
/
carbon or siliconÃ
/
oxygen bonds were
The formation of SiÃ
/
Si bonds (Ph2Me4Si2) was only
Ph2PCH2CH2NMe2]PtMe2
observed when [(k2-P,N)Ã
/
was reacted with ClSiMe2Ph. The platinum complex
acted as the chlorine scavenger in this stoichiometric
reaction [2]. In extending our investigations to analo-
gous reactions with organotin hydrides, we hoped to
gain more insight into the electronic and energetic
parameters that govern the outcome of a particular
It was hoped that a comparison of different platinum
complex catalysts would allow some conclusions on how
the ligands, especially hemilabile ligands, influence the
outcome of the reaction. For this purpose, the reactions
of the complexes Pt(acac)2 (acacꢀ
(1), (PhMe2P)2PtMe2 (2), (dppe)PtMe2 (dppeꢀ
phenylphosphino)ethane) (3), and the (PS N)PtMe2
complexes [(k2-P,N)Ã
Ph2PCH2CH2CH2NMe2]PtMe2
/
acetylacetonate)
/bis(di-
* Corresponding author. Tel.: ꢂ
58801 15399.
E-mail address: uschuber@mail.zserv.tuwicn.ac.at (U. Schubert).
/
43-1-58801 15320; fax: ꢂ43-1-
/
/
/
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01539-6

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S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
(PC3NPtMe2) (4) and [(k2-P,N)Ã
PtMe2 (PC2NPtMe2) (5), with triphenyltin hydride
(HSnPh3) and tri-n-butyltin hydride (HSnnBu3) were
investigated.
/
Ph2PCH2CH2NMe2]-
reactant stannanes was not achieved after 3 days at
room temperature.
2.2. Reaction with (PhMe2P)2PtMe2 (2)
On reaction of 2 with HSnPh3 or HSnBu3 there was
complete consumption of the reagent stannane within 24
2. Results and discussion
h at 2:HSnR3 ratios of 1:1ꢃ1:5 and 1:20. Analogous
/
complexes and tin species were observed with both tin
hydrides used, though rates of conversion to distannane
did alter.
When the stannanes were added to any of the three
platinum complexes, strong gas evolution occurred in all
cases, and the corresponding distannane, R3SnÃ
/
SnR3,
31P NMR spectra taken in the initial stages of the
reactions with either stannane showed the immediate
partial loss of the starting platinum complex and
formation of a new platinum complex, with satellites
from platinum and tin [6]. The phosphorus atoms of this
platinum complex in addition to be equivalent, exhibit a
typical cis-1J(PPt) coupling of 2443 Hz [7]. Both also
show cis- and a weak trans-PPtSn coupling, hence it
must be the bis(stannyl) complex, cis-(PhMe2P)2Pt-
was formed as the main product. The reactions were
monitored by 1H, 31P{1H} and 119Sn NMR spectro-
scopy and distinct differences were observed.
2.1. Reaction with Pt(acac)2 (1)
On addition of a stoichiometric amount, or a 20- or
100-fold excess of HSnPh3 to a benzene solution of 1,
crystals of the distannane Ph3SnÃ
/
SnPh3 were formed
(SnR3)2 (6a: Rꢀ
/
Ph, 6b: Rꢀn
Bu). In the case of
/
within 5 min. When a ratio of 1:20 was employed, about
85% of the stannane was converted to distannane during
HSnPh3 when ratios of 1:2 or greater were used, the
methyl/stannyl exchange at platinum occurs to an extent
of approximately 90% at room temperature within 60
min. When HSnBu3 was employed, 6b was only
identified in traces within this time period, the reasoning
for this will be discussed later. The mono-substituted
complex, (PhMe2P)2Pt(Me)SnR3 was not observed in
either case, it must therefore, be assumed that exchange
of the second methyl group proceeds faster then that of
the first.
At this point with HSnPh3, i.e., the first 60 min of the
reaction at room temperature, a maximum of three tin
species were present (HSnR3, Sn2R6 and 6a). At 1:1
ratios only 6a was observed, once the 1:2 ratio had been
reached, distannane was also present. In the case of
larger excesses, reactant stannane was still observed in
the 119Sn and 1H NMR spectra. No evidence was found
for the formation of MeSnPh3, thus indicating that the
methyl groups are eliminated as methane (see below).
1
this 5 min period (integration of H NMR spectra). In
the case of larger excesses, i.e. 1:100, the same products
were identified, but only roughly 20% conversion to
distannane was observed within 24 h at room tempera-
ture, determined from NMR spectra. Even after heating
at 60 8C for 3 h conversion to distannane was only about
30%. The starting tin hydride and Sn2Ph6 were the only
tin species identified throughout the course of the
reaction by NMR spectroscopy. In addition, 195Pt{1H}
NMR spectra only showed the presence of 1, and there
appeared to be no change of the acetylacetonate
coordination since no spectroscopic indication of de-
coordinated acetylacetone or h1-coordinate acetylaceto-
nate ligands was found. This indicates that the distan-
nane is formed via a radical mechanism.
Analogous results were obtained when HSnBu3 was
used as the reagent stannane except for reaction being
much faster. In the reaction of either stannane there was
no evidence of elemental platinum.
Experiments were also carried out in a similar manner
to those described but the two different tin hydrides,
HSnPh3 and HSnBu3, were added simultaneously in
equal amounts to 1 in a benzene solution. The total
platinum complex to tin hydride ratio was 1:40. The
main product were the homogeneous distannanes, i.e.
Sn2Ph6 and Sn2Bu6, although some asymmetric distan-
nanes were observed in addition to the original tin
hydrides. The preferred formation of the symmetrical
distannanes may be due to the different reactivity of
both stananes in radical reactions. No evidence was
found to suggest some sort of equilibrium between
asymmetrical distannanes and the, evidently favoured,
symmetrical distannanes. Complete consumption of the
With HSnBu3 at ratios of 1:1, Sn2Bu6 is the only tin
species observed, while 2 is still present. At higher ratios
complex 6b was observed. With longer reaction times
and ratios 1:2, traces of MeSnBu3 were observed. This
would imply that catalytic distannane formation must
occur already at this ratio (1:1). This could be dependent
on the stannane used HSnBu3 which has a weaker HÃ
/
Sn
bond than HSnPh3, and thus could facilitate the
formation of the distannane.

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331
The reaction of 2 with HSnR3 obviously proceeds in
two steps; the bis(stannyl) complexes 6 are formed first,
which then produce Sn2R6 in a catalytic reaction. The
difference in reactivity between HSnPh3 and HSnBu3
sence of a chelate ligand would influence the outcome of
the reaction. Therefore, the reactions of the bis-phos-
phine complex (dppe)PtMe2 (3) was also tested. The
reactivity of complex 3 may also serve as a reference for
implies that for Rꢀ
faster than the formation of 6, for Rꢀ
true.
At periods ꢀ
/
Bu the distannane formation is
that of (PS N)PtMe2 complexes discussed below.
/
/
Ph the opposite is
Within the first 10 min of the reaction, the reactant
platinum complex disappeared, and a new platinum
complex was formed. In accordance with what was
observed with 2, the corresponding complexes 9 (9a:
/
90 min, complexes 6a and 6b in turn
began to disappear, and a new complex 7b was formed
from 6b, and a new complex 8 from 6a. This can be
followed well in 31P NMR where the proportion of 6
decreases with formation of the new complexes 7b or 8.
In the 119Sn NMR spectrum a new peak can be assigned
to the new complexes. A consumption of the complex 6
was observed with both stannanes and at all ratios, but
to different extents. When an 1:20 ratio was employed,
transformation of 6 to 7b or 8 was complete after 24 h,
this coincides with the disappearance of the first new
platinum complex 6. With a lower stoichiometric ratio,
approximately 35% of 6 was consumed within 24 h.
One can imagine that complex 7 is formed through
addition of a HSnR3 group to complex 6, and then loss
Rꢀ
/
Ph, 9b: Rꢀn
Bu) were formed.
/
ð3Þ
This complex is well supported with NMR data. In
the 1H NMR spectrum, the methyl groups are no longer
present, for both HSnBu3 and HSnPh3 as reactant
stannane. In the 31P NMR spectrum, the characteristic
coupling between the tin atom and phosphorus is seen,
and this with tin atoms in both the cis and trans position
to phosphorus [6].
Reaction of 3 with the stannanes is slower than for 2.
Conversion to the corresponding distannane with com-
plex 3 in ratios of 1:20 after 3 h at room temperature was
only about 7 and 15% for HSnBu3 and HSnPh3,
respectively, compared with 90% for 2 with HSnBu3
and at least 23% for HSnPh3. Apart from this platinum
complex no further 31P NMR signals, and hence
platinum complexes were identified. Reactions at differ-
ent ratios or with either of the stannanes showed no
great difference in reactivity, or further products
formed.
of distannane, R3SnÃ
/
SnR3, occurs leaving 7. In the case
of HSnBu3 this complex 7b could be stable given work
carried out on analogous silicon complexes [8]. It could
be imagined that with aromatic substituents at tin (7a), a
rearranged complex of structure 8 would be more stable
due to the higher migration tendency of phenyl groups,
and to the more stable trans influence achieved through
the phenyl ligand compared with an alkyl group. Given
that complex 8 is the more stable form for RꢀPh and
/
that rearrangement occurs quickly, this would explain
the absence of spectroscopic evidence of 7a in both 31P
1
NMR and H NMR spectra.
(2)
The formation of complex 7 has been explained by
further addition of HSnR3, however in the lower ratios
NMR spectra imply the complete consumption of the
reactant stannane which poses a problem for its forma-
tion. It could be that dissolved hydrogen is still present
in solution but is not spectroscopically visible.
2.4. Reaction with (PS N)PtMe2 (4)
/
In contrast to reactions of 2 with HSnBu3 and
HSnPh3, where both stannanes resulted in analogous
reactions and products, the outcome of the reaction of
(PC3N)PtMe2 (4) depended slightly on the kind of
employed stannane.
When the reaction between 4 and HSnBu3 was carried
out in a stoichiometric ratio (1:1), the tin hydride had
completely reacted within the first 5 min (as monitored
by 1H NMR spectroscopy). Gas evolution was observed
2.3. Reaction with (dppe)PtMe2 (3)
If the reactions of 2 proceed via intermediates in
which a phosphine ligands is de-coordinated, the pre-

332
S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
Scheme 1.
2
on addition of the stannane, which must be methane,
considering the absence of other by-products. The only
tin species identified by 119Sn NMR spectroscopy were
distannane, MeBuSn3 and a platinum stannyl complex,
10b.
by H NMR spectroscopy. Here the platinum bonded
methyl groups of the reactant platinum complex were
easily identified. During the course of the reaction a new
CD3 group was identified, this could be assigned to the
remaining trans-methyl group at the platinum centre.
When the reaction between 4 and HSnPh3 was carried
out in a stoichiometric ratio (1:1), the tin hydride also
reacted completely within the first 5 min (as monitored
As soon as an 1:1 ratio was exceeded, complex 10b
was the major platinum species present and could be
identified immediately. This new platinum complex 10b,
and the reactant complex 4 were also identified by 195Pt
NMR spectroscopy which at this point (at 1:1 ratios,
after 2 h) gave no suggestion of further platinum species.
Complex 10b may be on the route to the formation of
the distannane. From the reactions of 4 with HSiR3 it is
known that the second methyl ligand is exchanged much
slower than the first [1], due to the different trans
influence of the coordinated nitrogen and phosphorus
atoms. It is reasonable to assume that the same is true
for the Me/SnR3 exchange. The fact that only 10b and
Sn2R6 are observed in the reaction mixture implies that
the intermediate bis(stannyl) complex leads to fast
formation of distannane. It is suggested that the reaction
mechanism is along the lines of Scheme 1, where the first
step is slow (initial addition of HSnR3, and loss of CH4),
and the next step, and generation of Sn2R6 (further
addition of HSnR3 and loss of H2 as shown in the
brackets) is much faster. Given that the reaction is
catalytic, the platinum complexes shown within the
brackets would only be present in very small amounts
for production of distannane, and given the timescale,
not spectroscopically visible.
1
by H NMR spectroscopy), but in this case Sn2Ph6 and
MeSnPh3 were identified by 119Sn NMR spectroscopy.
The occurrence of MeSnPh3 indicates a similar mechan-
ism as in the reaction of (PS
leading to mono- and bis-(silyl) complexes, (PS
N)Pt(SiR3)Me and (PS N)Pt(SiR3)2. In this reaction,
/N)PtMe2 with HSiR3
/
/
one methyl ligand was eliminated as methane and the
second as methylsilane [9]. At ratios from 1:1 to 1:4 no
reactant stannane was observed after 5 min. At stoichio-
metric ratios with HSnPh3, no new platinum complexes
were initially identified. However, after a period of 2 h, a
new platinum complex was observed, present in ap-
proximately the same ratio as the still present 4. This
new complex was also identified as the mono-substituted
platinum complex 10a.
When HSnPh3 was reacted in larger than stoichio-
metric ratios, further tin and platinum species were
observed. The main tin-containing product was still the
expected distannane, however three new platinum com-
plexes were observed by 31P NMR spectroscopy.
Among them is obviously 10a. Another complex is
almost certainly the phenyl substituted platinum com-
plex 11, and the final complex may be the bis(stannyl)
complex.
The remaining methyl group on platinum trans to
1
phosphorus can be tentatively assigned in the H NMR
spectrum at stoichiometric ratios. In order confirm that,
experiments were undertaken with CD3 groups on the
platinum complex instead of CH3 groups. In this case
the PC2N complex 5 instead of the PC3N complex 4 was
used. Initial control experiments were carried out with
the CH3 platinum complex. The results were analogous
to those found for complex 4. The reactions of
(PC2N)Pt(CD3)2 with HSnBu3 and with HSnPh3 were
carried out at stoichiometric ratios and was monitored
In addition to these platinum complexes, several other
tin compounds, such as MeSnPh3, Me2SnPh2 and
Me3SnPh were observed with NMR spectroscopy.
This phenomena was tested in separate experiments,
where 4 was reacted with MeSnPh3 and SnPh4 at room
temperature and then at 60 8C. The same individual
tetraalkylstannanes were observed as seen in the reac-
tion of 4 with HSnPh3. Here again complex 11 was also
observed in the 31P NMR spectrum, this was the same

S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ
/338
333
(4)
platinum complex, which was seen in the reaction with
HSnPh3. No further platinum complexes were identi-
fied. When this same reaction was carried out with 1 or 2
no reaction was observed.
with the (PS N)PtMe2 complex. At a 1:20 ratio, after 60
min at room temperature, reaction of 4 results in
approximately 97% of tin moieties as distannane (the
/
rest being PtÃ/Sn) compared with 90% with complex 2.
The reaction with the deuterated platinum complex 5
and HSnPh3 further supports these findings. Here
deuterated 10a was seen, and further CD3-substituted
organotin species were identified.
Complex 3 produces exactly analogous results as with
HSnPh3, though conversion to distannane is lower, 3%
at 60 min.
The compounds MexSnPh4ꢁx are obviously formed
by oxidative addition of SnÃ
/
Ph groups (SnÃ
/
Ph groups
are easier added than SnÃ
/
Me groups [10]) followed by
3. Conclusions
further redistribution reactions at the platinum centre.
The first observation when looking at the different
reactions is that HSnBu3 has a higher affinity to form
the distannane in the metal-catalysed reactions. This can
be seen throughout the course of the reactions, even in
the case of 1, which is considered to react via a different
reaction pathway.
2.5. Comparison of the platinum complexes
By examining the 31P NMR spectra of the reaction
mixtures with phosphorus-containing platinum com-
plexes it is possible to compare qualitatively the relative
reactivity of these complexes. The most obvious point is
Although the corresponding distannane is the main or
only tin-containing product in each case the results
that on reaction with HSnPh3 the (PS N)PtMe2 com-
/
plexes (4 and 5) immediately produce the corresponding
distannane from ratios of 1:1, while in the reactions of
the bis-phosphine complexes (2 and 3) the correspond-
ing bis(stannyl) complexes (6 and 9) are first observed
before distannane builds up. When comparing an 1:20
ratio 5 min into the reaction, in the case of 4 an
approximately 50% conversion to distannane is ob-
served compared only with 5% with 2. These figures
are only rough guides, especially in the case of Sn2Ph6,
which is poorly soluble in benzene. However, the trend
indicate that the platinum complexes Pt(acac)2, (PS
/
N)PtMe2 and (R3P)2PtMe2 react by different reaction
pathways with HSnPh3 and HSnBu3. Pt(acac)2 clearly
seems to react via a radical mechanism, which does not
appear to be the case with the other platinum com-
plexes. These obviously react by oxidative addition/
reductive elimination mechanisms, that involves ex-
change of the methyl ligands for stannyl groups. There
is strong evidence that bis(stannyl) complexes are
involved in the formation of the distannanes.
The results also show again the differences between
the bis-phosphine (2 and 3) and the P,N-chelated
complexes (4 and 5). In the latter complexes, the
differently activated methyl ligands result in different
is clear that the (PS N)PtMe2 complex 4 appears more
/
effective at producing distannane. Complex 3 is even less
efficient, where after 60 min at room temperature only
15% conversion has been observed. This would indicate,
in comparison with 2, that that some flexibility in the
platinum complex could be necessary for the addition of
the HSnPh3/loss of Sn2Ph6.
exchange rates. With the (PS
initially at least, only the methyl group trans to nitrogen
is exchanged as a result of the weaker PtÃC bond trans
to nitrogen. This is similar to the phenenoma seen with
the reaction of (PS N)PtMe2 complexes with the silicon
/N)PtMe2 complexes,
/
It is also interesting to note that the complexes 2ꢃ
not react in the same manner as 1. It still seems
Me complexes to react with the
/5 do
/
preferable for all PtÃ
/
analogues, where single substitution is always seen [1].
Furthermore, the effect of the hemilable chelating ligand
leads to several by-products, which originate from the
incoming HSnR3 by oxidative addition rather than
induce a radical type reaction.
The reaction with HSnBu3 to form distannanes
appears to be more favourable (probably due to reasons
activation of SnÃ/C bonds, at least in the case of
HSnPh3. Such rearrangement reactions were not ob-
served with the bis(phosphine) complexes 2 and 3, or
with 1.
discussed previously), though in both cases a platinumÃ
/
tin moiety is observed at some point during the reaction.
Even with this stannane a slight improvement is seen

334
S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
4. Experimental
the course of the reaction*/see text for noteworthy
integration comparisons.
All reactions were carried out using standard Schlenk
techniques in an argon atmosphere. Argon was purified
˚
using Cu and molecular sieve (4 A). All NMR measure-
4.2. Reaction of Pt(acac)2 (1) with HSnPh3
ments were carried out in deuterated benzene (C6D6),
the samples were filled and sealed in an argon atmo-
A) HSnPh3 (8.9 mg, 0.025 mmol) was added at r.t. to
10 mg (0.025 mmol) of 1 in 0.5 ml of C6D6. Light
gas evolution was observed.
sphere. Benzene-d6 was pre-dried using a molecular
˚
sieve (4 A) and then made oxygen-free using the freezeꢃ
/
B) HSnPh3 (178 mg, 0.51 mmol) was added at r.t. to 10
mg (0.025 mmol) of 1 in 0.5 ml of C6D6. Very strong
gas evolution was observed, and a yellow solution
was present. Distannane crystals began to form
after 15 min. They were collected and dried. Their
identity as Ph3SnSnPh3 was achieved through XRD
power diffraction in comparison with an authentic
sample. Crystal yield 149 mg (0.213 mmol, 84%).
C) HSnPh3 (133 mg, 0.38 mmol) was added at r.t. to
1.5 mg (0.004 mmol) of 1 in 0.5 ml of C6D6. The
sample turned yellow. Crystals of Ph3SnSnPh3 were
formed from the reaction solution within 24 h.
Crystal yield approximately 111 mg (0.088 mmol,
46%).
pumpꢃthaw method.
/
The tin hydrides used were either purchased from
Sigma Aldrich and in the case of HSnPh3 also prepared
from the corresponding chlorostannane using LiAlH4.
Purity was controlled using 1H and 119Sn NMR spectra.
The platinum complexes were prepared as reported in
the literature [11,9], the bis-phosphine complexes were
prepared as stated the literature except the platinum
reagent used was nbdPtCl2 (prepared as in Ref. [12]).
LiMe was used as methylating agent and diethyl-ether as
the solvent. Pt(acac)2 was purchased from Sigma
Aldrich and then made oxygen-free.
NMR experiments were taken on Bruker Avance 300
and 250 MHz spectrometers at room temperature (r.t.),
unless otherwise stated, using external standard (TMS,
85% H3PO4; Me4Sn and Na2Pt(H2O)6, respectively). All
pulse programs used were obtained from the standard
Bruker software library. Assignment of 119Sn NMR
signals was also based on HSn-HMQC experiments. 31P,
195Pt and 13C NMR spectra were proton decoupled, 1D
119Sn NMR spectra were obtained using the inversed
gated technique. 2H NMR experiments were carried out
using a standard ZG30 PULSE program without lock.
1H NMR:
4J(PtOCCH)ꢀ
lites, 4J(PtOCCH)ꢀ
with satellites, 1J(117SnH)ꢀ
Hz, HSn), 7.19ꢃ7.76 (m, H Ã
(ppm) ꢁ
d
(ppm) 1.59 (s, with satellites
128 Hz, Pt(OCCH3)), 5.09 (s with satel-
159 Hz, Pt(OCCHCO)), 7.01 (s
1849 Hz, 1J(119SnH)ꢀ
1934
PhSn); 119Sn{1H} NMR: d
141.6 (s, Ph3SnSnPh3);
/
/
/
/
/
/
/
163.2 (s, HSnPh3), ꢁ
/
13C{1H} NMR: d (ppm) 25.21 (s, Pt(OCCH3)), 102.85
(s, Pt(OCCHCO)), 129.14 (s with satellites, unresolved,
CarSnH), 129.33 (s with satellites, unresolved, (CarSn)2),
1
137.83 (s with sats), J(CC)ꢀ
/
5 Hz, CarSnH), 138.02 (t,
4 Hz, (CarSn)2), 185.47 (s, Pt(OCCH3));
1J(CC)ꢀ
195Pt{1H} NMR: d (ppm) ꢁ
/
4.1. General reaction procedure
/400.3 (s, Pt(acac)2).
The platinum complex was weighed into the NMR
tube (Schlenk tube) under argon and then dissolved/
suspended in C6D6. The stannane was then added at r.t.,
as quickly as possible via a syringe. At catalytic ratios,
the pure, undiluted stannane was added to the platinum
complex. At stoichiometric ratios, the stannane was
diluted with C6D6 and then added to the platinum
complex. The reaction was allowed to subside and then
immediately NMR spectra were taken. The reaction was
then followed by spectra taken at regular intervals.
All NMR signals seen throughout the course of the
reaction are given here, including those which are only
seen at certain ratios or specific reaction times, e.g. in
some cases the reagent peaks are only seen in the
stoichiometric reaction mixtures or at the beginning of
a reaction. Further specific information is given in the
main text. The majority of peaks are seen throughout
the course of the reaction, and only the intensity of a few
specific signals alter. For these reasons chemical shifts
are given without integration as this varies throughout
4.3. Reaction of Pt(acac)2 (1) with HSnBu3
A) HSnBu3 (5.9 mg, 0.020 mmol) was added at r.t. to 8
mg (0.020 mmol) of 1 in 0.5 ml of C6D6. After 90
min at r.t., in which time NMR spectra were taken
in regular intervals, another equivalent of HSnBu3
(5.9 mg, 0.020 mmol) and the process repeated (ca.
90min). A further equivalent was then added, and
the process repeated again until a ratio of 1:5 was
achieved.
B) HSnBu3 (148 mg, 0.5 mmol) was added at r.t. to 10
mg (0.025 mmol) of 1 in 0.5 ml of C6D6. On
addition of the stannane, hefty gas evolution was
observed, and a colouring of the solution to yellow.
After 75 min at r.t., another 20 equiv. of HSnBu3
(148 mg, 0.5 mmol) was added, more gas evolution
was observed and the spectrum remained un-
changed except for the corresponding integrals in
1H NMR.

S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ
/338
335
3
1H NMR: d (ppm) 1.07 (t, J(HCCH)ꢀ
Bu), 1.20ꢃ1.32 (t(1.23)ꢂ 7.2 Hz, H Ã
m, 3J(HCCH)ꢀ
Bu), 1.51 (sxt, 3J(HCCH)ꢀ
7.5 Hz, H ÃBu), 1.58 (s,
/
7.3 Hz, H Ã
/
satellites, 1J(PtP)ꢀ
(PhMe2P)2Pt(SnPh3)2 (6a), ꢁ
1J(PtP)ꢀ
1796 Hz, cis-PÃPtSn, (6a), ꢁ
satellites, 1J(PtP)ꢀ
1981 Hz, tr-PÃ
119Sn{1H} NMR: d (ppm) ꢁ
9.46 (s, PtÃ
141.5 (s, SnÃSn), 229.9 (s, HPhSn Ã
195Pt{1H} NMR: d (ppm) ꢁ
/
2443 Hz, 2J(SnPtP)ꢀ
/
184 Hz,
/
/
/
/
/
55.66 (s with satellites,
56.71 (s with
PtSn, (6a);
Sn, 6a),
Pt, 8a);
4586.4 (t, J(PPt)ꢀ1819
4971.2 (t, J(PPt)ꢀ2662 Hz, tr-(PhMe2P)2-
5340.8 (t, J(PPt)ꢀ2442 Hz, 6a)
/
/
/
/
/
3
Pt(OCCH3)), 1.75 (quinꢂ
/
m, J(HCCH)ꢀ
/
8.1 Hz, H Ã
/
/
/
Bu), 5.09 (s, Pt(OCCHCO)); 119Sn{1H} NMR: d (ppm)
/
/
1
ꢁ
/
83.48 (s with satellites, J(SnH)ꢀ
/
2492 Hz, SnÃ
/
Sn);
ꢁ
/
/
ꢁ
/
/
13C{1H} NMR: d (ppm) 10.44 (s with satellites,
1J(CC)ꢀ40 Hz, 1J(C117Sn)ꢀ230 Hz 1J(C119Sn) ꢀ
240 Hz, CBu Sn), 13.70 (s with satellites,
2J(CC117/119Sn)ꢀ
, CBu Sn), 24.75 (s, Pt(OCCH3)),
27.66 (s with satellites, 1J(CC)ꢀ
54 Hz, CBu Sn),
39.90 (t, 1J(C117/119Sn)ꢀ
8.2 Hz, CBu Sn), 102.30 (s,
Pt(OCCHCO)), 184.86 (s, Pt(OCCH3)); 195Pt{1H}
NMR: d (ppm) ꢁ400.3 (s, Pt(acac)2).
/
/
1
1
/
/
/
Hz, 2), ꢁ
Pt(SnPh3)2), ꢁ
/
/
1
Ã
/
/
/
/
Ã
/
/
Ã
/
4.6. Reaction of (PhMe2P)2PtMe2 (2) with HSnBu3
/
Ã
/
A) HSnBu3 (5.8 mg, 0.0199 mmol) was added at r.t. to
10 mg (0.0199 mmol) of 2 in 0.5 ml of C6D6. After
90 min at r.t., in which time NMR spectra were
taken, another equivalent of HSnBu3 (5.8 mg,
0.0199 mmol) and the process repeated, (ca. 90
min). A further equivalent was then added, and the
process repeated again until a ratio of 1:5 was
achieved.
/
4.4. Reaction of Pt(acac)2 (1) with HSnBu3 and
HSnPh3
Seven hundred and thirty nine milligram (2.54 mmol)
of HSnBu3 and 892 mg (2.54 mmol) of HSnPh3 were
added at r.t. to 5 mg (0.013 mmol) of 1 in 0.5 ml of
C6D6. On addition of the stannane a slight colouring of
the solution to yellow was observed. NMR spectra were
recorded.
After being left a RT for 5d crystals were formed,
whose identity was confirmed to be Sn2Ph6 through a
powder XRD analysis.
B) Fifty eight milligram (0.199 mmol) of HSnBu3 was
added at r.t. to 5 mg (0.0099 mmol) of 2 in 0.5 ml of
C6D6.
1H NMR: d (ppm) 0.94ꢃ
(m, H ÃBu, H Ã
MePt), 1.09 (t, 3J(HCCH)ꢀ
Bu), 1.25ꢃ1.38 (m, H ÃBu, H ÃMePt), 1.49ꢃ1.59 (m, H Ã
Bu, H ÃMePt), 1.52 (sxt, J(HCCH)ꢀ7.7 Hz, H ÃBu),
1.74ꢃ1.85 (m, H ÃBu), 5.08 (quin with satellites,
2J(HSnC)ꢀ
1.9 Hz,
1J(H119Sn)ꢀ
7.46ꢃ7.59 (m, H Ã
/
1.01 (m, H Ã
/
Bu), 1.05ꢃ
7.3 Hz, H Ã
/
/1.11
/
/
/
/
/
/
/
/
3
/
/
/
119Sn{1H} NMR: d (ppm) ꢁ
(s, Sn ÃSn, Sn2Bu6), ꢁ
HSnBu3), ꢁ129.8 (s, SnBu/Ph), ꢁ
Ph3), ꢁ163.0 (s, with satellites, Sn Ã
/
68.4 (s, SnBu/Ph) ꢁ
89.2(s, with satellites, Sn Ã
148.3 (s, Ph3SnSn-
H, HSnPh3).
/
84.5
/
/
/
/
/H,
/
1J(H117Sn)ꢀ
/
1517
Hz,
/
/
/
1590 Hz, H Ã
/
Sn), 7.08ꢃ
/
7.10 (m, H Ã
/
PhP),
/
/
/
/
PhP); 31P{1H} NMR: d (ppm)
1
ꢁ
/
10.03 (s, with satellites, J(PtP)ꢀ
/
1821 Hz, 2), ꢁ
44.04 (s, 7b);
Sn), ꢁ6.4 (s,
/6.7
(s with satellites, 1J(PtP)ꢀ
119Sn{1H} NMR: d (ppm) ꢁ
MeSnBu3), ꢁ12.3 (s, PtÃSn).
/
2816 Hz, 6b), ꢁ
84.1 (s, SnÃ
/
/
4.5. Reaction of (PhMe2P)2PtMe2 (2) with HSnPh3
/
/
/
A) Seven milligram (0.0199 mmol) of HSnPh3 was
added at r.t. to 10 mg (0.0199 mmol) of 2 in 0.5
ml of C6D6. After 90 min at r.t., in which time
NMR spectra were taken, another equivalent of
HSnBu3 (7.0 mg, 0.0199 mmol) and the process
repeated (ca. 90min). A further equivalent was then
added, and the process repeated again until a ratio
of 1:5 was achieved.
B) One hundred and forty milligram (0.4 mmol) of
HSnPh3 was added at r.t. to 10 mg (0.0199 mmol) of
2 in 0.5 ml of C6D6. After being left a RT for 7d
crystals were formed, whose identity was confirmed
to be Sn2Ph3 through a powder XRD analysis.
/
4.7. Reaction of (dppe)PtMe2 (3) with HSnPh3
Fifty six milligram (0.16 mmol) of HSnPh3 was added
at r.t. to 5 mg (0.008 mmol) of 3 in 0.5 ml of C6D6.
3
1H NMR: d (ppm) 1.72ꢃ
/
1.85 (m, J(HCP)ꢀ
/
9.5 Hz,
1849 Hz,
7.08 (m, H ÃPhP),
PhSn); 31P{1H} NMR: d
(ppm) 58.63 (s, with satellites, 1J(PtP)ꢀ
2263 Hz,
2J(tr-117SnPtP)ꢀ1577 Hz, 2J(tr-119SnPtP)ꢀ
1598 Hz,
2J(cis-117SnPtP)ꢀ119 Hz, 2J(cis-119SnPtP)ꢀ
144 Hz,
9a); 119Sn{1H} NMR: d (ppm) ꢁ
46.1 (s, SnÃPt, 9a),
141.6 (s, SnÃSn), ꢁ163.2(s, Sn ÃH, HSnPh3).
C2H4) 7.02 (s with satellites, 1J(117SnH)ꢀ
1J(119SnH)ꢀ
1934 Hz, H ÃSn), 7.02ꢃ
7.51ꢃ7.80 (m, H ÃPhP/H Ã
/
/
/
/
/
/
/
/
/
/
/
/
/
1H NMR: d (ppm) 0.9ꢃ
/
1.0 (m, H Ã
/
MePt), 1.68 (t with
2.84 Hz, J(HCPPt)ꢀ34 Hz, H Ã
MeP), 7.01 (s with satellites, 1J(117SnH)ꢀ
1849 Hz,
1J(119SnH)ꢀ
1934 Hz, HSn), 7.08ꢃ7.10 (m, H ÃPhP),
7.46ꢃ7.59 (m, H Ã
PhP); 31P{1H} NMR: d (ppm)
9.81(s, with satellites, 2660 Hz,
1J(PtP)ꢀ
(PhMe2P)2Pt(SnPh3)2 (6a), ꢁ10.03 (s, with satellites,
1J(PtP)ꢀ
1821 Hz, (PhMe2P)2PtMe2 (2), ꢁ12.89 (s with
/
/
2
3
satellites, J(HCP)ꢀ
/
/
/
ꢁ
/
/
/
/
/
/
/
/
4.8. Reaction of (dppe)PtMe2 (3) with HSnBu3
/
/
ꢁ
/
/
A) HSnBu3 (4.7 mg, 0.016 mmol) was added at r.t. to
10 mg (0.016 mmol) of 3 in 0.5 ml of C6D6. After 90
min at r.t., in which time NMR spectra were taken,
/
/
/

336
S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
3
another equivalent of HSnBu3 (4.7 mg, 0.016 mmol)
and the process repeated (ca. 90 min). A further
equivalent was then added, and the process repeated
again until a ratio of 1:4 was achieved.
1H NMR: d (ppm) 1.09 (t, J(HCCH)ꢀ
Bu), 1.25ꢃ1.33 (m, H ÃMePt/H ÃBuSn), 1.54 (sxt,
3J(HCCH)ꢀ
7.2 Hz, H ÃBu), 1.78 (sxt, J(HCCH)ꢀ
7.5 Hz, H ÃBu), 1.8ꢃ2.2 (m, PC2H4N), 2.36 (s with
satellites, J(PtNCH)ꢀ17.9 Hz, NÃ(CH3)2), 7.09ꢃ7.21
(m, H ÃPhP), 7.80ꢃ7.85 (m, H Ã
PhP); 31P{1H} NMR: d
(ppm) 36.33 (s, with satellites, 1J(PtP)ꢀ
2072 Hz,
PC2NPtMe2 (5); 119Sn NMR: d (ppm) ꢁ
84.04 (s,
Sn ÃSn), ꢁ6.9 (s, Sn Ã
Pt); 195Pt{1H} NMR: d (ppm)
4046 (d, J(PPt)ꢀ2095 Hz, PC2NPtMe2 (5).
/
7.4 Hz, H Ã
/
/
/
/
3
/
/
/
/
/
3
B) HSnBu3 (46.7 mg, 0.16 mmol) was added at r.t. to 5
/
/
/
mg (0.008 mmol) of 3 in 0.5 ml C6D6.
/
/
/
/
1H NMR: d (ppm) 0.9ꢃ
1.40ꢃ1.55 (m, H ÃBu), 1.61ꢃ
1.91ꢃ2.02 (m, J(HCCP)ꢀ
/
1.6 (m, H Ã
/
Bu, HÃ
/
MePt),
/
/
/
/
1.76 (m, H Ã
/
Bu/H Ã
/
MePt),
/
/
/
3
1
/
/
8.2 Hz, C2H4), 5.18 (quin
1.9 Hz, 1J(H117Sn)ꢀ
1517
PhP),
ꢁ
/
/
with satellites, 2J(HSnC)ꢀ
/
/
1
Hz, J(H119Sn)ꢀ
/
1590 Hz, H Ã
/
Sn), 7.13 (m, H Ã
/
4.11. Reaction of (PC2N)Pt(CD3)2 (5) with HSnBu3
1
7.77 (t, J(HC)ꢀ
/
6.8 Hz, H Ã
/
PhP); 31P{1H} NMR: d
1
(ppm) 48.11 (s, with satellites, J(PtP)ꢀ
/
1778 Hz, 3),
2124 Hz, 9b);
14.5 (s, SnÃPt, 9b),
H, HSnBu3).
Fifteen milligram (0.052 mmol) of HSnBu3 was added
at r.t. to 13 mg (0.027 mmol) of (PC2N)Pt(CD3)2 in 0.5
ml of C6D6. Light gas evolution and a colour change to
56.62 (s, with satellites, 1J(PtP)ꢀ
119Sn{1H} NMR: d (ppm) ꢁ
84.5 (s, SnÃSn), ꢁ89.2(s, Sn Ã
/
/
/
ꢁ
/
/
/
/
pinkꢃ
/
brown was observed.
3
1H NMR: d (ppm) 1.09 (t, J(HCCH)ꢀ
/
7.3 Hz, H Ã
/
3
4.9. Reaction of (PC3N)PtMe2 (4) with HSnBu3
Bu), 1.25ꢃ
7.4 Hz, H Ã
PC2H4N), 2.37 (s with satellites, J(PtNCH)ꢀ
NÃ(CH3)2), 7.15ꢃ7.17 (m, H ÃPhP), 7.79ꢃ7.85 (m, H Ã
PhP) 2H NMR: d (ppm) 0.46 (s, with satellites,
3J(PtCD)ꢀ
52.0 Hz, D-MePt, (PC2NPt(CD3)(SnBu3)),
1.52(d, with satellites, J(HD)ꢀ
Hz, D-MePt, 5?D), 1.79(d, with satellites, 2J(HD)ꢀ
Hz, 2J(PtCD)ꢀ12.2 Hz, D-MePt, 5?D); 31P{1H} NMR:
d (ppm) 36.33 (s, with satellites, 1J(PtP)ꢀ
2072 Hz,
5?D); 119Sn NMR: d (ppm) ꢁ
84.07 (s, Sn ÃSn), ꢁ7.0 (s,
Sn Ã
Pt); 195Pt{1H} NMR: d (ppm) ꢁ4046 (d, 1J(PPt)ꢀ
2095 Hz, PC2NPtMe2).
/
1.33 (m, H Ã
/
BuSn), 1.54 (sxt, J(HCCH)ꢀ
Bu), 1.91ꢃ2.07 (m,
17.9 Hz,
/
/
Bu), 1.72ꢃ1.83 (m, H Ã
/
/
/
A) HSnBu3 (5.86 mg, 0.02 mmol) was added at r.t. to
10 mg (0.02 mmol) of 4 in 0.5 ml of C6D6. After 90
min at r.t., in which time NMR spectra were taken,
another equivalent of HSnBu3 (7.1 mg, 0.02 mmol)
and the process repeated (ca. 90 min). A further
equivalent was then added, and the process repeated
again until a ratio of 1:5 was achieved.
B) Fifty eight-milligram (0.2 mmol) of HSnBu3 was
added at r.t. to 5 mg (0.01 mmol) of 4 in 0.5 ml of
C6D6. On addition of the stannane, very strong gas
evolution was observed.
3
/
/
/
/
/
/
/
2
/
1.0 Hz, 2J(PtCD)ꢀ
0.95
/
9.6
/
/
/
/
/
/
/
/
/
1H NMR: d (ppm) 0.95ꢃ
(m, H ÃBu), 1.40ꢃ1.86 (m, H Ã
PC3H6N), 2.43 (s with satellites, 3J(PtNCH)ꢀ
/
1.14 (m, H Ã
/
Bu), 1.22ꢃ
2.33(m,
18 Hz
(CH3)2), 5.08 (quin with satellites, J(HSnC)ꢀ1.9
1590 Hz, H Ã
7.94 (tt, H ÃPhP);
31P{1H} NMR: d (ppm) 15.27 (s, with satellites,
/
1.32
4.12. Reaction of (PC3N)PtMe2 (4) with HSnPh3
/
/
/
Bu), 1.99ꢃ
/
/
2
A) HSnPh3 (274.8 mg, 7.8 mmol) was added at r.t. to
34 mg (7.8 mmol) of 4 in 5 ml of C6D6.
NÃ
/
/
Hz, J(H117Sn)ꢀ
/
1517 Hz, J(H119Sn)ꢀ
/
/
1
1
B) HSnPh3 (7.1 mg, 0.02 mmol) was added at r.t. to 10
mg (0.02 mmol) of 4 in 0.5 ml of C6D6. After 75 min
at r.t., in which time NMR spectra were taken,
another equivalent of HSnPh3 (7.1 mg, 0.02 mmol)
and the process repeated (ca. 90 min). A further
equivalent was then added, and the process repeated
again until a ratio of 1:5 was achieved. After being
left a RT for 3d crystals were formed, whose
identity was confirmed to be Sn2Ph3 through a
powder XRD analysis.
C) HSnPh3 (42 mg, 0.12 mmol) was added at r.t. to 3
mg (0.006 mmol) of 4 in 0.5 ml of C6D6. After being
left a RT for 3d crystals were formed, whose
identity was confirmed to be Sn2Ph3 through a
powder XRD analysis.
Sn), 6.99ꢃ7.55 (m, H Ã
/
/
PhP), 7.75ꢃ
/
/
1J(PtP)ꢀ
/
2088 Hz, 4), 16.97 (s with satellites,
2158 Hz, 10b); 119Sn{1H} NMR: d (ppm)
1J(PtP)ꢀ
/
ꢁ
/
84.04 (s, SnÃ
/
Sn), ꢁ
/
6.57 (s, MeSnBu3), ꢁ
/
12.6 (s, PtÃ
Pt), 9.89
Sn), 25.32
13 Hz, PC3H6N), 28.09
58 Hz, CBu Sn), 29.83 (d,
12 Hz, PC3H6N), 31.34 (s, CBu
NCH3), 126.17 (s, CarÃP), 131.33 (s, CarÃ
NMR: d (ppm) ꢁ4051 (d, J(PPt)ꢀ
/
Sn, 10b); 13C{1H} NMR: d (ppm) 9.25 (s, CMe
Ã
/
(s, CMe
(s, CMe
Ã
/
Pt), 10.61 (s, CBu
Pt), 27.92 (d, J(PC)ꢀ
Ã
/
Sn), 14.12 (s, CBu
Ã
/
1
Ã
/
/
1
(s with satellites, J(SnC)ꢀ
/
Ã
/
1J(PC)ꢀ
/
Ã
/
Sn), 45.31 (s,
/
/
P); 195Pt{1H}
1
/
/
1032 Hz, 4).
4.10. Reaction of (PC2N)PtMe2 (5) with HSnBu3
3
Eleven milligram (0.039 mmol) of HSnBu3 was added
at r.t. to 9.5 mg (0.020 mmol) of 5 in 0.5 ml of C6D6.
1H NMR: d (ppm) 1.05 (d, J(PPtCH)ꢀ
/
7.5 Hz, tr-
8.5
CH3 (4), 1.29 (d, with
3
PtÃ
/
CH3, (10a), 1.12 (d, with satellites, J(PPtCH)ꢀ
/
Light gas evolution and a colour change to pinkꢃ
/
brown
Hz, 2J(PtCH)ꢀ
/
88 Hz, tr-PtÃ
/
3
2
was observed.
satellites, J(PPtCH)ꢀ
/
7.6 Hz, J(PtCH)ꢀ32 Hz, cis-
/

S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ
/338
337
PtÃ
(m, PC2H4CH2N), 2.43 (s with satellites, J(PtNCH)ꢀ
(CH3)2, (4), 2.71 (s with satellites,
/
CH3, (4), 1.89ꢃ
/
2.09 (m, PC2H4CH2N), 2.25ꢃ
/
2.28
(ppm) 10.69 (s with satellites, 1J(PtP)ꢀ
PC2NPt(CD3)Ph), 16.50 (s, PC2NPt(CD3)(SnPh3))
/
2660 Hz,
3
/
1
18 Hz, NÃ
3J(PtNCH)ꢀ
H Ã
PhP), 7.04 (s with satellites, J(H117Sn)ꢀ
1J(H119Sn)ꢀ
1935 Hz, H ÃSn), 7.11ꢃ
7.53ꢃ7.77 (m, H ÃPhSn), 7.80ꢃ7.86 (m, H Ã
/
28.51 (s, with satellites, J(PtP)ꢀ
NMR: d (ppm) ꢁ141.1 (s, Ph3SnSnPh3), ꢁ
SnPh4), ꢁ90.5 (s, MeSnPh3).
/
4550 Hz, 5?D); 119Sn
126.9 (s,
/
12.6 Hz, NÃ
/
(CH3)2, (10a), 6.86ꢃ
/
6.99 (m,
/
/
1
/
/
1849 Hz
/
/
/
/
7.24 (m, H Ã
/
PhP),
/
/
/
/PhP);
31P{1H} NMR: d (ppm) 10.67 (s with satellites,
4.15. Reaction of (PC3N)PtMe2 (4) with SnPh4
1J(PtP)ꢀ
1J(PtP)ꢀ
1J(PtP)ꢀ
/
1901 Hz, 11), 12.76 (s with satellites,
1978 Hz, 10a), 13.69 (s with satellites,
1978 Hz, PC3NPt(SnPh3)2), 15.27 (s, with
/
SnPh4 (8.6 mg, 0.02 mmol) was added at r.t. to 10 mg
(0.02 mmol) of 4 in 0.5 ml of C6D6. After 5 h at r.t., the
sample was heated over night at 60 8C which then
/
satellites, 1J(PtP)ꢀ
(ppm) ꢁ148.3 (s, Ph3SnSnPh3), ꢁ
MeSnPh3), ꢁ59.9 (s, Me2SnPh2), ꢁ
2.3 (s, Sn Ã
Pt, 10a); 195Pt{1H} NMR: d (ppm) ꢁ
(d, 1J(PPt)ꢀ 3844 (d, 1J(PPt)ꢀ
1043 Hz, 4), ꢁ 1985 Hz,
10a).
/
2088 Hz, 4); 119Sn{1H} NMR: d
127.5 (s,) ꢁ91.6 (s,
30.8 (s, Me3SnPh),
4038
/
/
/
resulted in a reaction.
3
/
/
1H NMR: d (ppm) 0 (d, J(PPtCH)ꢀ
/
0 Hz, tr-PtÃ
8.5 Hz,
CH3 (PC3NPtMe2)), 1.29 (d,
/
3
ꢁ
/
/
/
CH3 (4), 1.12 (d, with satellites, J(PPtCH)ꢀ
2J(PtCH)ꢀ
88 Hz, tr-PtÃ
with satellites, J(PPtCH)ꢀ
cis-PtÃCH3 (PC3NPtMe2)),
PC2H4CH2N), 2.25ꢃ
with satellites, 3J(PtNCH)ꢀ
(PC3NPtMe2)), 6.86ꢃ6.99 (m, H Ã
H ÃPhP), 7.53ꢃ7.77 (m, H ÃPhSn), 7.80ꢃ
PhP); 31P{1H} NMR: d (ppm) 10.67 (s with satellites,
1J(PtP)ꢀ1907 Hz, PC3NPtMePh); 119Sn{1H} NMR: d
(ppm) ꢁ127.1 (s, SnPh4), ꢁ91.2 (s, MeSnPh3), ꢁ60.7
(s, Me2SnPh2), ꢁ30.5 (s, Me3SnPh), ꢁ2.3 (s, Sn ÃPt).
/
/
/
/
/
/
3
2
/
7.6 Hz, J(PtCH)ꢀ
/32 Hz,
/
1.89ꢃ2.09
/
(m,
4.13. Reaction of (PC2N)PtMe2 (5) with HSnPh3
/
2.28 (m, PC2H4CH2N), 2.43 (s
18 Hz, NÃ(CH3)2
PhP), 7.11ꢃ7.24 (m,
7.86 (m, H Ã
/
/
HSnPh3 (7.28 mg, 0.02 mmol) was added at r.t. to 10
mg (0.02 mmol) of 5 in 0.5 ml of C6D6. Slight gas
evolution was observed. After being left a RT for 7d
crystals were formed, whose identity was confirmed to
be Sn2Ph3 through a powder XRD analysis.
/
/
/
/
/
/
/
/
/
/
/
/
1H NMR:
3J(PPtCH)ꢀ7.7 Hz, 2J(PtCH)ꢀ
(5), 1.59 (d, with satellites, 3J(PPtCH)ꢀ
2J(PtCH)ꢀ
91 Hz, cis-PtÃCH3 (PC2NPtMe2)), 1.71ꢃ
1.75 (m, PCH2CH2N and satellites), 1.90ꢃ2.02 (m,
PCH2CH2N), 2.36 (s with satellites, J(PtNCH)ꢀ17.6
Hz, NÃ(CH3)2 (5), 7.07ꢃ7.18 (m, HÃPhP), 7.04 (s with
satellites, J(H117Sn)ꢀ1849 Hz J(H119Sn)ꢀ
1935 Hz,
HÃSn), 7.51ꢃ7.87 (m, H ÃPhP/H Ã
PhSn); 31P{1H}
NMR: d (ppm) 10.64 (s with satellites, 1J(PtP)ꢀ
2659.5 Hz, PC2NPtMe(SnPh3)), 36.33 (s, with satellites,
1J(PtP)ꢀ2072 Hz, 5); 119Sn NMR: d (ppm) ꢁ
141.6 (s,
Ph3SnSnPh3), ꢁ91.05 (s, MeSnPh3).
d
(ppm) 1.33 (d, with satellites,
67 Hz, tr-PtÃCH3
7.3 Hz,
/
/
/
/
/
/
/
/
/
/
4.16. Reaction of (PC3N)PtMe2 (4) with MeSnPh3
/
3
/
MeSnPh3 (7.4 mg, 0.02 mmol) was added at r.t. to 10
mg (0.02 mmol) of 4 in 0.5 ml of C6D6. After 5 h at r.t.,
the sample was heated over night at 60 8C which then
resulted in a reaction.
/
/
/
1
1
/
/
/
/
/
/
/
1H NMR:
2J(HC117Sn)ꢀ
d
52
(ppm) 0.15 (s, with satellites,
Hz, 65 Hz,
2J(HC119Sn)ꢀ
/
/
/
/
(H3C)2SnPh2), 0.64 (s, with satellites, 2J(HC117Sn)ꢀ
/
2
/
64 Hz, J(HC119Sn)ꢀ
/
67 Hz, H3CSnPh3), 1.12 (d, with
2
3
satellites, J(PPtCH)ꢀ
/
8.5 Hz, J(PtCH)ꢀ88 Hz, tr-
/
3
4.14. Reaction of (PC2N)Pt(CD3)2 (5) with HSnPh3
PtÃ
/
CH3, (4), 1.29 (d, with satellites, J(PPtCH)ꢀ
/7.6
2
Hz, J(PtCH)ꢀ
PC2H4CH2N), 2.25ꢃ
satellites, 3J(PtNCH)ꢀ
6.99 (m, H ÃPhP), 7.11ꢃ
(m, H ÃPhSn), 7.80ꢃ7.86 (m, H Ã
d (ppm) 10.67 (s with satellites, J(PtP)ꢀ
119Sn{1H} NMR: d (ppm) ꢁ
90.1 (s, MeSnPh3), ꢁ
(s, Me2SnPh2), ꢁ30.5 (s, Me3SnPh), ꢁ1.9 (s, Sn ÃPt).
/
32 Hz, cis-PtÃ
/
CH3, 4), 1.89ꢃ/2.09 (m,
HSnPh3 (7.2 mg, 0.02 mmol) was added at r.t. to 10
mg (0.02 mmol) of 5 in 0.5 ml of C6D6.
/
2.28 (m, PC2H4CH2N), 2.43 (s with
18 Hz, NÃ(CH3)2, (4), 6.86ꢃ
7.24 (m, H ÃPhP), 7.53ꢃ7.77
PhP); 31P{1H} NMR:
/
/
/
1H NMR: d (ppm) 1.71ꢃ
/
1.79, (m, PCH2CH2N),
2.04 (m, PCH2CH2N), 2.37 (s with satellites,
3J(PtNCH)ꢀ
17.9 Hz, NÃ(CH3)2, 5?D), 2.71 (s with
satellites, 13.0 Hz, NÃ(CH3)2,
3J(PtNCH)ꢀ
PC2NPt(SnPh3)Me), 6.91ꢃ7.23 (m, HÃPhP), 7.04 (s
with satellites, 1J(H117Sn)ꢀ
1935 Hz, HÃSn), 7.51ꢃ7.65 (m, H Ã
(m, H Ã
Hz, D-MeSn), 0.79 (s, with satellites, 3J(PtCD)ꢀ
/
/
/
/
1.91ꢃ
/
/
/
/
1
/
/
/1901 Hz, 11);
/
/
/
/60.1
/
/
/
/
/
/
1849 Hz 1J(H119Sn)ꢀ
/
/
/
/
PhP), 7.80ꢃ
/
7.87
/
PhSn); 2H NMR: d (ppm) 0.40 (d, 2J(HD)ꢀ
/1.9
/7.8
Acknowledgements
Hz, D-MePt, PC2NPt(CD3)(SnPh3)), 1.43 (d, with
satellites, 2J(HD)ꢀ1.0 Hz, 2J(PtCD)ꢀ
9.4 Hz, D-
MePt, 5?D), 1.70 (d, with satellites, J(HD)ꢀ0.98 Hz,
2J(PtCD)ꢀ14.2 Hz, D-MePt, 5?D); 31P{1H} NMR: d
/
/
Financial support by the Fonds zur Forderung der
¨
wissenschaftlichen Forschung (FWF), Austria is grate-
fully acknowledged.
2
/
/

338
S.M. Thompson, U. Schubert / Inorganica Chimica Acta 350 (2003) 329ꢃ338
/
[7] C.M. Haar, S.P. Nolan, W.J. Marshall, K.G. Moloy, A. Prock,
W.P. Giering, Organometallics 18 (1999) 474.
[8] F. Ozawa, J. Organomet. Chem. 611 (2000) 332.
[9] (a) J. Pfeiffer, G. Kickelbick, U. Schubert, Organometallics 19
(2000) 62;
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¨
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¨
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