Chelate-Assisted Oxidative Addition of Phenyl- and Alkyltin Groups to Nickel and Platinum

Article abstract of DOI:10.1002/(SICI)1099-0682(199807)1998:7<897::AID-EJIC897>3.0.CO;2-V

Reaction of Ni(COD)₂ (COD = 1,5-cyclooctadiene) with two equivalents of Ph₂PCH₂CH₂SnPh₃ or of (Ph₃P)₂Pt(C₂H₄) with two equivalents of Ph₂PCH₂CH₂SnR₃ (R = Ph, Me, Bu) results in the immediate formation of the complexes (R₃SnCH₂CH₂Ph₂P)M[PPh ₂CH₂CH₂SnPh₂(M-Sn)](R) (M = Ni, Pt) with a cis arrangement of the two phosphorus atoms. The structure of (Me₃SnCH₂CH₂Ph₂P)Pt[PPh ₂CH₂-CH₂SnMe₂(Pt-Sn)](Me) was confirmed by an X-ray structure analysis. In the presence of PPh₃, this complex shows dynamic behavior in solution due to Ph₂PCH₂CH₂SnMe₃/ PPh₃ exchange. When the phosphanylalkylstannanes Ph₂PCH₂CH₂SnPh_3-xMe_x (x = 1, 2) are employed in the reaction with Ni(COD)₂ or (Ph₃P)₂Pt(C₂H₄), the Sn-Ph groups are more prone to oxidative addition than the Sn-Me groups. When Ni(COD)₂ is treated with one equivalent of Ph₂PCH₂CH₂SnPh₃ and PR′₃ (PCy₃ or PMe₂Ph) each, the complexes (R′₃P)M(PPh₂CH₂CH₂SnPh ₂)(Ph)(M-Sn) are formed. Heating of (Ph₃SnCH₂CH₂Ph₂P)Ni[PPh ₂-CH₂CH₂SnPh₂(M-Sn))(Ph) to 70°C induces the oxidative addition of a Sn-Ph group of the dangling ligand, and cis-Ni[PPh₂CH₂CH₂SnPh₂(Ni-Sn)] ₂ is obtained. The same complex is formed upon reaction of Ni(COD)₂ with Ph₂PCH₂CH₂SnPh₂H. Reaction of Ni(COD)₂ with Ph₂PCH₂CH₂SnMe₃ results in the immediate formation of trans-Ni[(PPh₂CH₂CH₂SnMe ₂(Ni-Sn)]₂.

Full text of DOI:10.1002/(SICI)1099-0682(199807)1998:7<897::AID-EJIC897>3.0.CO;2-V

FULL PAPER
Transition Metal Stannyl Complexes, 12[᭛]
Institut für Anorganische Chemie, Technische Universität Wien,
Getreidemarkt 9, A-1060 Wien, Austria
Fax: (internat.) ϩ 43(0)1/5816668
E-mail: uschuber@fbch.tuwien.ac.at
Received January 19, 1998
Platinum / Nickel / Stannyl complexes / Oxidative addition / Tin
Reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with two are more prone to oxidative addition than the Sn–Me groups.
equivalents of Ph2PCH2CH2SnPh3 or of (Ph3P)2Pt(C2H4) with When Ni(COD)2 is treated with one equivalent of
two equivalents of Ph2PCH2CH2SnR3 (R = Ph, Me, Bu) results Ph2PCH2CH2SnPh3 and PR’3 (PCy3 or PMe2Ph) each, the
in the immediate formation of the complexes complexes
(R3SnCH2CH2Ph2P)M[PPh2CH2CH2SnPh2(M–Sn)](R) (M formed.
Ni, Pt) with a cis arrangement of the two phosphorus atoms. CH2CH2SnPh2(Ni–Sn)](Ph) to 70 °C induces the oxidative
The structure of (Me3SnCH2CH2Ph2P)Pt[PPh2CH2- addition of a Sn–Ph group of the dangling ligand, and cis-
(R’3P)M(PPh2CH2CH2SnPh2)(Ph)(M–Sn)
are
=
Heating of (Ph3SnCH2CH2Ph2P)Ni[PPh2-
CH2SnMe2(Pt–Sn)](Me) was confirmed by an X-ray structure Ni[PPh2CH2CH2SnPh2(Ni–Sn)]2 is obtained. The same
analysis. In the presence of PPh3, this complex shows complex is formed upon reaction of Ni(COD)2 with
dynamic behavior in solution due to Ph2PCH2CH2SnMe3/ Ph2PCH2CH2SnPh2H.
Reaction
of
Ni(COD)2
with
PPh3 exchange. When the phosphanylalkylstannanes Ph2PCH2CH2SnMe3 results in the immediate formation of
Ph2PCH2CH2SnPh3–xMex (x = 1, 2) are employed in the trans-Ni[(PPh2CH2CH2SnMe2(Ni–Sn)]2.
reaction with Ni(COD)2 or (Ph3P)2Pt(C2H4), the Sn–Ph groups
Contrary to SnϪH bonds that readily add to a variety
of transition-metal complex fragments,[2] there are only few
examples for the oxidative addition of non-activated SnϪC
When Ni(COD)2 (COD ϭ 1,5-cyclooctadiene) was
treated with two equivalents of Ph2PCH2CH2SnPh3 in
bonds. For example, SnPh4 only adds to electron-rich frag-
THF, the color of the yellow solution changed to deep or-
ments such as (Ph3P)2Pt to give (Ph3P)2Pt(SnR3)(Ph).[3][4][5]
ange, and a broad signal in the 31P-NMR spectrum at δ ഠ
SnϪMe bonds are even less reactive than SnϪPh bonds.[6]
28 indicated the immediate formation of phosphanenickel
complexes. Additional stirring for 2.5 h resulted in the al-
The weaker SnϪC bonds in alkynylstannanes also add to
less electron-rich metal centers.[7][8]
most quantitative formation of the oxidative addition prod-
uct (Eq. 1) according to the 31P-NMR spectrum.
One of the possibilities to promote oxidative addition re-
actions is “chelate assistance”, introduced by Stobart et al.
for phosphanylalkylsilyl ligands with SiϪH bonds.[9] We
previously used this option to add SnϪC bonds to electron-
rich Pd and Pt fragments[10] as well as to the less reactive
Fe(CO)4 fragment,[11] using ligands of the type
Ph2P(CH2)nSnR3. Richmond et. al. observed reversible
SnϪPh addition in the reaction of a SnPh3-substituted
ethylenediamine derivative with W(CO)3(CH3CN)3.[12] The
concept was also extended to SiϪSi and SiϪSn bonds.[13][14]
In the present paper, we first describe the reaction of
Ni(COD)2 with Ph2PCH2CH2SnR3. The results led us to
re-examine some of our experiments with Pt compounds
and to correct some of our previous results.[10]
We were not able to separate traces of
Ph2P(O)CH2CH2SnPh3 and unreacted Ph2PCH2CH2-
SnPh3. However, the structure of the complex was un-
equivocally confirmed by multinuclear NMR spectroscopy.
The spectra are discussed in detail in the following para-
graph because they are representative for most of the com-
plexes reported in this paper.
[᭛]
Part 11: Ref.[1]
.
Eur. J. Inorg. Chem.
, 897Ϫ903
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1434Ϫ1948/98/0707Ϫ0897 $ 17.50ϩ.50/0
897

H. Gilges, U. Schubert
FULL PAPER
The 31P{1H}-NMR spectrum of showed the expected
two doublet signals of an AB system. The resonance at δ ϭ
58.3 is attributed to the phosphorus atom in a five-mem-
bered ring because of the significant downfield shift of ca.
32 ppm relative to the resonance of the other phosphorus
nucleus at δ ϭ 26.1. This downfield shift is a well-known
phenomenon upon chelation,[15] and was also observed in
[9]
the related Pt complexes Pt[Ph2PCH2CH2SiR2(PtϪSi)]2
and (Ph3P)Pt(Ph2PCH2CH2SiR2)(SiR3)(PtϪSi).[13] The
2JPNiP coupling constant of 6.1 Hz proved the cis dispo-
sition of the phosphorus nuclei. The J117/119SnP coupling formed in 90% yield (31P NMR) together with and a
constant of 219.8 Hz between the Sn and P nucleus at δ ϭ small amount of PhP(O)Me2 as by-products.
58.3 of the chelate ring is typical for the cis position of both
nuclei. On the other hand, the signal at δ ϭ 26.1 showed
Unfortunately, was even more difficult to purify than
. The reaction of PCy3 resulted in almost quantitative for-
the typical trans-2JSnNiP 117Sn: 1065.9 Hz; 119Sn: 1109.3 mation of (Cy3P)Ni(Ph2PCH2CH2SnPh2)(Ph)(NiϪSn) ( )
(
Hz) and an additional set of Sn satellites attributed to the (31P-NMR). It was possible to isolate the complex analyti-
3J117/119SnCCP coupling within the dangling ligand. The cally pure as a yellow-brown powder by column chromatog-
NMR data confirm the trans position of the non-chelated raphy. Contrary to , it was even possible to assign the res-
ligand and the metal-bonded tin atom. The 119Sn-NMR onance for the ipso-carbon atom of the metal-bonded
2
spectrum corroborates the assignment of the phosphorus phenyl group. It appears at δ ϭ 155.6 (dd) with two JPNiC
resonances by showing a doublet of doublets at δ ϭ 23.6 couplings of 59.2 and 7.9 Hz due to the trans- and cis-phos-
2
for the tin atom bound to nickel, with trans J119SnNiP of phorus nuclei. These values are in good agreement with
1116.9 Hz and JSnP of 223 Hz. This resonance is distinctly those found for the ipso-carbon atom in (Me3P)2-
shifted downfield by ca. 120 ppm relative to the resonance Ni[CH2C(CH3)2C6H4(NiϪC)] (δ ϭ 171.1, trans-2JPNiC
at δ ϭ Ϫ97.6 for the non-coordinated SnPh3 group. This 79 Hz).[16]
ϭ
resonance appears as a doublet with the appropriate
In the reaction with Ph2PCH2CH2SnPh3, nickel re-
sembles platinum and does not parallel the reactivity pat-
3J119SnCCP of 183.8 Hz.
1
The H-NMR spectrum lacked essential structural in- tern of palladium that formed the product of a double oxi-
formation because the methylene proton signals appear as dative SnPh addition and consecutive reductive biphenyl
complex multiplets superimposing each other (see Exper- elimination,
trans-Pd[Ph2PCH2CH2SnPh2(PdϪSn)]2.[10]
imental Section). The only interesting feature is the reso- Therefore, the possibility to induce a second SnPh oxidative
ance of the protons of the Ni-bonded phenyl group. Their addition was probed. Crude was dissolved in toluene and
multiplet was significantly shifted to higher field (δ ϭ heated to about 70°C for 9 h. Monitoring the reaction by
6.75Ϫ7.05), compared to the other phenyl resonances. 31P-NMR spectroscopy showed a new singlet resonance at
This highfield shift seems to be a typical phenomenon for δ ϭ 63.3 with a double set of tin satellites. The coupling
complexes of this kind because it is also reported for (CO)3- constants of 930.1 Hz (119Sn), 891.0 Hz (117Sn), and 161.1
Fe(Ph2PCH2CH2SnPh2)(Ph)(FeϪSn)[11] and (Ph3P)Pt- Hz (119/117Sn) are in the typical range for a trans- and a cis-
(Ph2PCH2CH2SnPh2)(Ph)(PtϪSn).[10] The 13C-NMR tin nucleus relative to the phosphorus atoms, thus excluding
spectrum confirms that there are two different phosphanyl- trans-Ni[Ph2PCH2CH2SnPh2(NiϪSn)]2.
alkylstannane units in the molecule because of two sepa-
The singlet resonance in the 31P-NMR spectrum is due
rate resonances for the SnCH2 and the PCH2 group. While to two equivalent phosphorus nuclei in molecules where
the resonances for the methylene carbon atoms of the dan- both tin atoms are 118Sn isotopes. A doublet-of-doublet res-
gling ligand appear as doublets due to the coupling with onance at δ ϭ 56.8 was observed (trans-J119SnP ϭ 933.3 and
the phosphorus atom within the ligand, the resonances of cis-J119SnP ϭ 164.0 Hz) in the 119Sn-NMR spectrum. Even
the CH2 groups of the chelating ligand appear as doublet if one takes into account that the values given for the coup-
of doublets because of the additional coupling with the lings are based on a first-order interpretation of the spectra
other phosphorus nucleus. This observation seems reason- because the resolution was too poor to observe all coup-
able if one takes into account that in this case the second lings needed for a interpretation as an ABXY spin system,
phosphorus atom is in a kind of transoid position with the data clearly indicate the formation of the cis product
respect to the carbon nuclei while in the first case the sec- resulting from the oxidative addition of a second SnϪPh
ond phosphorus nucleus is cisoid. In the very complex bond (Eq. 3). Unfortunately, the course of the reaction was
range of the phenyl carbon signals no assignment for the not completely straightforward because some decompo-
ipso-carbon atom of the metal-bonded phenyl group was sition occurred, and the resulting product still contained
possible.
small amounts of besides the impurities present in the
Since the second Ph2PCH2CH2SnPh3 in just acts as a starting complex.
monodentate ligand, we also treated Ni(COD)2 with a 1:1
We therefore prepared independently from Ni(COD)2
mixture of Ph2PCH2CH2SnPh3 and PPhMe2 or PCy3 (Eq. with two equivalents of Ph2PCH2CH2SnPh2H, utilizing the
2). (PhMe2P)Ni(Ph2PCH2CH2SnPh2)(Ph)(NiϪSn) ( ) was fact that SnϪH bonds are more prone to oxidative addition
898
Eur. J. Inorg. Chem.
, 897Ϫ903

Transition Metal Stannyl Complexes, 12
FULL PAPER
than SnϪC bonds. On addition of the phosphanylalkylstan- phosphorus atoms in molecules with a 118Sn and a 119Sn
nane at room temperature, the color of the solution nucleus. The triplet pattern is caused by the fact that 2JSnNiP
changed immediately, and gas evolution was observed after and the “mixed” 2JSnNiP/3JSnCCP coupling constant have ap-
a short period. The yellow oil resulting after work-up proximately the same value. Thus, in the case of
showed the same resonances in the 31P- and 119Sn-NMR Ph2PCH2CH2SnMe3, the outcome of the reaction of
spectra as were observed in the thermal reaction of . This Ni(COD)2 parallels that of Pd.
proves that for SnH the second oxidative addition is facili-
tated, as expected (Eq. 3).
Comparing the higher reactivity of SnϪPh bonds with
that of SnϪMe it is somewhat surprising that elevated tem-
peratures are needed to induce oxidative addition of a sec-
ond SnϪPh bond while the addition of a second SnϪMe
bond takes place at room temperature. This may have steric
reasons. Steric effects may also be responsible for the for-
mation of different isomers in both reactions. In the reac-
tion of the SnPh3 derivative, the stereochemical outcome
of the reaction is probably controlled by electronic reasons
because all atoms bonded to the Ni center are equally sub-
stituted by phenyl groups. Contrary to that, steric factors
may dominate in the reaction of the trimethylstannyl de-
rivative, leading to the trans arrangement that minimizes
the steric repulsion between the bulkier phosphane sub-
stituents.
The ligand Ph2PCH2CH2SnPh2Me offers the possibility
of either SnϪPh or SnϪMe addition. Unfortunately, the
reaction carried out as before was not straightforward.
Nevertheless, the evolution of small amounts of gas was
observed during the reaction. The 31P-NMR spectrum of
the residue after work-up showed two characteristic doublet
resonances at δ ϭ 57.9 and 25.3 (2JPNiP ϭ 6.1 Hz) for the
main product. The reasonably close agreement of the NMR
In
the
reaction
of
Pd(PPh3)4
with
either
Ph2PCH2CH2SnPh3 or Ph2PCH2CH2SnMe3, the trans
complexes Pd[PPh2CH2CH2SnR(PdϪSn)]2 were formed.[10]
Because of the somewhat surprising formation of the cis
product
from
at elevated temperatures the question
arises which isomer is obtained when Ph2PCH2CH2SnMe3
is treated with Ni(COD)2 (Eq. 4).
2
data with those of (δ ϭ 58.3, 26.1; JPNiP ϭ 6.1 Hz) sug-
gested that (MePh2SnCH2CH2Ph2P)Ni[(PPh2CH2CH2-
SnPhMe)(NiϪSn)](Ph) with a dangling phosphanylalkyl-
stannane ligand is the main product. The tin satellites at
the downfield signal with JSnP ϭ 213 Hz supported this
interpretation. However, due to the poor resolution of the
spectrum no tin satellites at the highfield signal were ob-
served. A compound with a singlet resonance at δ ϭ 42.5
was formed as a minor product. No tin satellites were re-
The 31P-NMR spectrum of the residue obtained after re- solved at this signal, but it can be supposed that due to
moval of all volatiles showed two resonances. The one at the chemical shift and the gas evolution observed during
δ ϭ 30.6 with an Sn coupling of 149 Hz was assigned to reaction, trans-Ni[Ph2PCH2CH2SnPh2(NiϪSn)]2 may be
Ph2P(O)CH2CH2SnMe3 as shown by the 31P-NMR spec- the by-product.
trum of a sample of Ph2P(O)CH2CH2SnMe3, independ-
The somewhat different results for the oxidative addition
ently prepared by oxidation of the phosphane with H2O2. of SnϪC bonds to Ni0 compared to Pd0 and the fact that
Despite of the fact that all solvents were thoroughly dried we had found complexes of the type (R3Si-
and degassed, and air was excluded as far as possible by SiR2CH2CH2Ph2P)Pt[PPh2CH2CH2SiR2(PtϪSi)](SiR3) in
standard Schlenk techniques, it was impossible to suppress our previous investigations on chelate-assisted SiϪSi oxi-
the formation of phosphane oxides completely. The fact dative addition to (Ph3P)2Pt(C2H4), we re-checked the
that Ni0 complexes, that are intermediates in the reactions, experiments on the SnϪC addition of phosphanylalkylstan-
are very good catalysts in the phosphane oxidation by oxy- nanes to Pt0 published by us some years ago.[10] First, we
gen may be the reason that even very small traces of air led treated (Ph3P)2Pt(C2H4) with two molar equivalents of
to significant phosphane oxidation. The singlet resonance Ph2PCH2CH2SnPh3 according to the published procedure
at
δ
ϭ
41.5 was assigned to trans-Ni[Ph2PCH2- and observed almost quantitative formation of a complex
CH2SnMe2(NiϪSn)]2 because of the typical cis coupling to with the 31P-NMR data in good agreement with those
117/119Sn of 137.9 Hz and the equivalence of the two phos- previously assigned to (Ph3P)Pt[Ph2PCH2CH2SnPh2-
phorus nuclei (if both are 118Sn). The trans conformation (PtϪSn)](Ph) as product of this reaction. However, on scrut-
was confirmed by the virtual triplet observed in the 119Sn inizing the better data obtained now, we have to correct
spectrum at δ ϭ 5.9 due to the inequivalence of the two the assignment. Instead of the PPh3 derivative, the complex
Eur. J. Inorg. Chem.
, 897Ϫ903
899

H. Gilges, U. Schubert
FULL PAPER
(Ph3SnCH2CH2Ph2P)Pt[PPh2CH2CH2SnPh2(PtϪSn)](Ph)
( ) was formed (Eq. 5).
To elucidate the role of the PPh3 in the dynamic process,
was independently prepared from Pt(COD)2. As expected,
the product formed in almost quantitative yield showed
no dynamic features at room temperature because of the
absence of PPh3. On addition of PPh3, a dynamic process
was initiated similar to that observed for the product re-
sulting from the reaction of (Ph3P)2Pt(C2H4) at room tem-
perature.
Colorless crystals of suitable for an X-ray crystal struc-
ture analysis were obtained by diffusion of heptane into a
concentrated benzene solution of the complex. The struc-
ture analysis proved the cis arrangement of the two phos-
phorus ligands with one dangling phosphanylalkylstannane
This is confirmed by the fact that a coupling to Sn (179.9 (Figure 1). The PtϪC(1) distance [214 (1) pm] is in the nor-
3
Hz) in the typical range for a JSnCCP was now observed at mal range for PtϪCH3 compounds (202Ϫ220 pm).[18]The
the resonance for the phosphorus of the non-chelated li- PtϪSn(1) bond length of 259.36(8) pm is significantly
gand. The 119Sn-NMR spectrum also corroborates that shorter than that in trans-(Ph3P)2Pt(SnPh3)(H) (265.4
there is a dangling phosphanylalkylstannane ligand because pm).[19] This difference is reasonable if one takes into ac-
there is an additional doublet at δ ϭ Ϫ97.5 with the correct count the different influence of a hydride and a phosphane
phosphorus coupling besides the doublet of doublets reso- ligand. The P(1)ϪPtϪP(2) angle is widened [104.30(9)°] due
nance for the chelated tin nucleus at δ ϭ 97.2. Complex
to the steric repulsions between the bulky phenyl groups
corresponds to the analogous Ni complex . It therefore at the phosphorus atoms. This distortion from the regular
seemed reasonable to study whether a second oxidative square-planar arrangement is compensated by the angles
SnϪPh addition is also possible for Pt. However, a toluene C(1)ϪPtϪP(2), C(1)ϪPtϪSn(1) and P(1)ϪPtϪSn(1) being
solution of heated to 70°C for 10 h and then analyzed by smaller than 90° [87.8(3), 85.3(3), and 82.55(7)°]. The latter
31P-NMR spectroscopy did not indicate any formation of is partially due to chelation. The methyl groups at the tin
the product of a second oxidative addition.
atom of the dangling ligand are disordered in the crystal.
This led us to re-examine also the reaction of two equiva-
lents Ph2PCH2CH2SnMe3 with (Ph3P)2Pt(C2H4), for which
we had previously postulated the formation of the PtIV
complex Pt[PPh2CH2CH2SnMe2(PtϪSn)]2(Me)2.[10] On in-
spection of the better spectroscopic data obtained now we
realized that the formerly observed doublet resonance in the
119Sn-NMR spectrum is contradicting the proposed struc-
ture. The product was instead the PtII complex
(Me3SnCH2CH2Ph2P)Pt[PPh2CH2CH2SnMe2(PtϪSn)]-
(Me) ( ) (Eq. 5). The spectrum of the yellow oil left after
removal of all volatiles from the reaction mixture mainly
showed two broad resonances at δ ഠ 55 and 27, and a
broad signal at δ ϭ Ϫ3 in the 31P-NMR spectrum. The
signals sharpened on lowering the temperature, and at 240
K the dynamic process was completely frozen. At this tem-
Figure 1. ORTEP diagram of ; the hydrogen atoms are omitted
for clarity[a]
perature, the expected spectrum for
the typical AB pat-
tern with the corresponding Sn satellites, was observed in
addition to a sharp resonance for free PPh3. The fact that
the resonances of the dangling phosphorus ligand and the
PPh3 continually broaden on rising the temperature from
240 K to 360 K while the resonance of the ring-integrated
phosphorus first broadens to a much smaller extend, and
[a]
Selected bond lengths [pm] and angles [°]: PtϪC(1) 213.7(11),
PtϪP(1) 227.4(3), PtϪP(2) 232.7(3), PtϪSn(1) 259.36(8),
then re-sharpens (starting at about 310 K) indicates that the Sn(1)ϪC(2) 213.7(11), P(1)ϪC(3) 184.5(10), P(2)ϪC(4) 187.2(9),
Sn(2)ϪC(5) 213.1(10), Sn(1)ϪC(33) 213.0(11), Sn(1)ϪC(34)
dynamic process is a Ph2PCH2CH2SnMe3/PPh3 exchange at
215.0(12); C(1)ϪPtϪP(1) 167.4(3), C(1)ϪPtϪP(2) 87.8(3),
the PtII center. This suggestion is in agreement with results
P(1)ϪPtϪP(2) 104.30(9), C(1)ϪPtϪSn(1) 85.3(3), P(1)ϪPtϪSn(1)
82.55(7), P(2)ϪPtϪSn(1) 173.13(7), C(33)ϪSn(1)ϪC(34) 104.4(5),
C(33)ϪSn(1)ϪC(2) 109.2(5), C(34)ϪSn(1)ϪC(2) 106.4(5), C(33)Ϫ
Sn(1)ϪPt 118.2(3), C(34)ϪSn(1)ϪPt 115.6(4), C(2)ϪSn(1)ϪPt
102.5(3), C(24)ϪP(2)ϪPt 110.8(3), C(18)ϪP(2)ϪPt 115.3(4),
C(4)ϪP(2)ϪPt 121.3(4), C(12)ϪP(1)ϪC(3) 103.7(5), C(6)Ϫ
P(1)ϪC(3) 100.2(4), C(12)ϪP(1)ϪPt 114.6(3), C(6)ϪP(1)ϪPt
120.0(4), C(5)ϪC(4)ϪP(2) 114.8(7), C(3)ϪC(2)ϪSn(1) 107.9(8),
C(2)ϪC(3)ϪP(1) 113.2(7), C(4)ϪC(5)ϪSn(2) 113.9(7).
obtained for the complexes cis-(Ph3P)2Pt(SiR3)(H) where
similar interchange processes with excess PPh3 were ob-
served[17]. The authors also observed the phenomenon that
the resonance of the PPh3 ligand cis to the silyl ligand that
does not take part in the dynamic process is only slightly
broadened.
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Eur. J. Inorg. Chem.
, 897Ϫ903

Transition Metal Stannyl Complexes, 12
FULL PAPER
Attempts to induce the oxidative addition of one of the ductive elimination of biphenyl from the intermediate NiIV
SnMe bonds of the dangling ligand by heating a toluene complex.
solution of to about 90°C for 10 h failed. The 31P-NMR
In the corresponding reactions of the trimethylstannyl de-
spectrum did not indicate any reaction.
rivative Ph2PCH2CH2SnMe3 the reactivity pattern of
Contrary to the results obtained for Ni0, an increase of Ni(COD)2 parallels that of Pd(PPh3)4. In both cases the bis-
the steric bulk at the Sn atom by changing the methyl chelated complexes trans-M[PPh2CH2CH2SnMe2(MϪSn)]2
groups in the phosphanylethylstannane against butyl were formed, while the reaction with (Ph3P)2Pt(C2H4)
groups did not influence the general outcome of the reac- stopped at the stage of the mono-chelated complex cis-
tion. Besides the main product (Bu3SnCH2CH2Ph2P)Pt- (Me3SnCH2CH2Ph2P)Pt[(PPh2CH2CH2SnMe2)(PtϪSn)](Me)
[PPh2CH2CH2SnBu2(PtϪSn)](Bu) ( ) (formed in 90% yield ( ). The change in geometry of Ni[PPh2CH2CH2SnMe2-
according to the 31P-NMR spectrum), a minor amount of (NiϪSn)]2 compared to the SnPh2 derivative ( ) is probably
(Ph3P)Pt[PPh2CH2CH2SnBu2(PtϪSn)](Bu) was observed caused by steric effects overriding the electronic preference
as a by-product [31P NMR(C6D6): δ ϭ 53.9 (d, 2JPPtP ϭ 9.7 of the cis isomer.
1
Hz, J117/119SnP ϭ 105.0 Hz, JPtP ϭ 1914.1 Hz), 32.1 (d,
When the phosphanylalkylstannanes Ph2PCH2CH2-
SnPh3ϪxMex (x ϭ 1, 2) are employed, there is the possibil-
ity of either SnϪPh or SnϪMe oxidative addition. For both
2JPPtP ϭ 9.7 Hz, J119SnNiP ϭ 1666.3 Hz, J117SnPtP
ϭ
2
2
1
1597.9, JPtP ϭ 2119.2].
The use of the previously unknown derivative Ni0 and Pt0, the SnϪPh groups are more prone to oxidative
Ph2PCH2CH2SnMe2Ph, synthesized similar to its con- addition than the SnϪMe groups, as was previously ob-
geners by radical addition of PhMe2SnH to CH2ϭCHPPh2, served by us for Fe complexes.[11]
led to the formation of (PhMe2SnCH2CH2Ph2P)Pt-
[PPh2CH2CH2SnMe2(PtϪSn)](Ph) ( ) and thus corrobor-
ates the fact that SnPh addition is favored over SnMe ad-
Complex , whose structure was unambiguously con-
firmed by an X-ray structure analysis, showed dynamic be-
havior in the presence of PPh3 that may be attributed to a
PPh3/Ph2PCH2CH2SnMe3 exchange process.
dition. The exclusive formation of the product of SnϪPh
activation was proven in the 1H-NMR spectrum by a
This work was supported by the Fonds zur Förderung der wissen-
slightly broadened singlet resonance for the methyl groups
schaftlichen Forschung (FWF). We thank Dr. K. Mereiter for valu-
at the metal-bonded Sn with a coupling to platinum of 7.3
able discussions.
Hz. This coupling constant was too small a value for
3
2JPtCH, but in good agreement with a JPtSnCH coupling.
The proton signals of the PtϪPh moiety once again show
All operations were carried under dry and oxygen-free argon by
the significant high-field shift and appear at δ ϭ 6.87Ϫ6.98.
standard Schlenk-tube techniques. All solvents were dried by stand-
The 13C-NMR spectrum in the range for the sp2-carbon
atoms and their Pt satellites is very complex. Therefore, no
assignments are possible. The complexes and are not
dynamic at room temperature in the presence of PPh3.
ard procedures, saturated with argon and stored over molecular
sieves. The THF used was freshly distilled from potassium. The
phosphanylalkylstannanes were synthesized according to literature
procedures[11][20] from Ph2P(C2H3) and HSnR3. Ϫ The NMR spec-
tra were recorded with a Bruker AC 250 spectrometer. 1H- and 13C-
NMR data were referenced against the solvent resonances, while
31P- and 119Sn-NMR data were referenced against the external
standards 85% H3PO4 and SnMe4. Integrations of the 1H-NMR
signals are omitted if there are overlaps with residual proton reso-
nances of the deuterated solvents (especially C6D6). Ϫ DSC analy-
ses were performed with a Shimadzu Thermal Analyzer DSC 50.
The expression JXY is used for those cases where coupling is pos-
sible through different nuclei.
The present and our previous results on corresponding
palladium complexes,[10] allow to draw a complete picture
on the reactivity pattern of Ph2PCH2CH2SnR3 (R ϭ Me,
Ph) with complexes of the zero-valent metals of the nickel
triad. For R ϭ phenyl, the reactivity of Ni(COD)2 parallels
that of (Ph3P)2Pt(C2H4). Complexes of the type
(Ph3SnCH2CH2Ph2P)M[PPh2CH2CH2SnPh2(MϪSn)](Ph)
[M ϭ Ni ( ), Pt ( )], with a dangling Ph2PCH2CH2SnR3
ligand and a cis disposition of the two phosphorus atoms,
were formed in both cases. For the nickel complex , the
oxidative addition of an SnϪPh bond of the dangling
Preparation of (Ph3SnCH2CH2PPh2)Ni(Ph)[Ph2PCH2CH2-
SnPh2(NiϪSn)] ( ): An amount of 922 mg (1.63 mmol) of
Ph2PCH2CH2SnPh3 was added to a solution of 213 mg (0.77
mmol) of Ni(COD)2 in 25 ml of THF. The color of the yellow
solution immediately turned to deep orange. After additional 2.5 h
Ph2PCH2CH2SnR3 ligand was observed at elevated tem- of stirring at room temperature, the reaction mixture was yellowish
brown. Then the solvent and most of the COD was removed in
vacuo at 40°C, leaving a slightly oily golden brown residue that
contained as the main product, according to the 31P-NMR spec-
trum. Neither recrystallisation nor column chromatography on sil-
ica with common organic solvents resulted in analytically pure
samples of . Ϫ 31P NMR (101.25 MHz, C6D6): δ ϭ 58.3 (d,
peratures during which the cis arrangement of the phos-
phorus atoms was retained. The resulting complex is cis-
Ni[PPh2CH2CH2SnPh2(NiϪSn)]2 ( ). The same reaction
was not observed for the corresponding Pt complex . The
higher reactivity of Ni for the formation of the second che-
late ring by oxidative addition of an SnϪPh bond of the
dangling phosphanylalkylstannyl ligand is somewhat sur-
prising, because the heavier metals in a group are more
prone to oxidative addition reactions. The driving force for
2
2JPNiP ϭ 6.1 Hz, J117/119SnP ϭ 219.8 Hz), 26.1 (d, JPNiP ϭ 6.1 Hz,
2
3
2J119SnNiP ϭ 1109.3 Hz, J117SnNiP ϭ 1065.9 Hz, JSnCCP ϭ 183.0
Hz). Ϫ 119Sn NMR (93.276 MHz, C6D6) δ 23.6 (dd, JSnNiP
ϭ
2
1116.7 Hz, JSnP ϭ 223 Hz), Ϫ97.6 (d, JSnCCP ϭ 183.8 Hz). Ϫ 13C
3
2
the formation of from therefore may be the easier re- NMR (62.90 MHz, C6D6): δ ϭ 3.9 (d, SnCH2, JPCC ϭ 5.1 Hz),
Eur. J. Inorg. Chem.
, 897Ϫ903
901

H. Gilges, U. Schubert
FULL PAPER
2
6.3 (dd, SnCH2, JPCC ϭ 31.7 Hz, JPC ϭ 13.4 Hz), 23.7 (d, PCH2, During additional 3 h of stirring, the color of the solution lightened
1
1JPC ϭ 11.5 Hz), 32.6 (dd, PCH2, JPC ϭ 24.5 Hz, JPC ϭ 7.9 Hz), to yellowish brown with further weak gas evolution. Then all vol-
127.8Ϫ146.5 (C6H5). Ϫ 1H NMR (250.130 MHz, C6D6): δ ϭ atiles were removed in vacuo leaving a yellowish brown oily residue
1.01Ϫ1.38 (m, overlapping SnCH2), 1.59Ϫ1.84 (m, PCH2), containing in about 85% yield, as confirmed by 31P- and 119Sn-
2.40Ϫ2.61 (m, PCH2), 6.75Ϫ7.05 (m, NiC6H5), 7.00Ϫ7.62 (m, NMR spectroscopy. Washing the residue twice with 3 ml of pentane
C6H5).
each left a slightly oily yellowish brown powder that still contained
some impurities that could not be removed. Ϫ 31P NMR (101.250
MHz, C6D6): δ ϭ 63.3 (s, 2J119SnNiP ϭ 930.5 Hz, 2J117SnNiP ϭ 891.1
Hz, J117/119SnP ϭ 161.1 Hz. Ϫ 119Sn NMR (93.276 MHz, C6D6):
Preparation of (PhMe2P)Ni(Ph)[Ph2PCH2CH2SnPh2(NiϪ
Sn)] ( ): A solution of 51 mg (0.37 mmol) of PhPMe2 and 207 mg
(0.37 mmol) of Ph2PCH2CH2SnPh3 in 6 ml of THF was added to
a solution of 101 mg (0.37 mmol) of Ni(COD)2 in 10 ml of THF.
The mixture turned orange and, during further stirring for 4 h,
yellow-brown. After removal of all volatiles, a sticky yellowish
brown residue was obtained. It contained 90% of and some
2
δ ϭ 56.8 (dd, JPNiSn ϭ 933.3 Hz, JSnP ϭ 164.0 Hz).
Reaction of Ni(COD)2 with Ph2PCH2CH2SnMe3: A solution of
1.47 g (3.86 mmol) of Ph2PCH2CH2SnMe3 in 8 ml of THF was
added to a solution of 532 mg (1.93 mmol) of Ni(COD)2 in 40 ml
of THF. The resulting red solution was stirred for 3 h during which
a gas evolved and the color of the solution deepened. The red-
brown solution was concentrated in vacuo, and the resulting yel-
low-brown slightly sticky residue was analyzed by 31P- and 119Sn-
NMR spectroscopy. Ϫ 31P NMR (101.250 MHz, C6D6): δ ϭ 41.5
(s, JSnP ϭ 137.9 Hz). Ϫ 119Sn NMR (93.276 MHz, C6D6): δ ϭ
5.9 (t).
and PhP(O)Me2 according to the NMR spectra. Ϫ 31P NMR
(101.25 MHz, C6D6): δ ϭ 60.0 (d, JPNiP ϭ 4.2 Hz, J117/119SnP
2
ϭ
2
2
239.0 Hz), Ϫ6.8 (d, JPNiP ϭ 4.2 Hz, J119SnNiP ϭ 1199.5 Hz,
2J117SnNiP ϭ 1150.3 Hz). Ϫ 119Sn NMR (93.276 MHz, C6D6): δ ϭ
35.0 (dd, JSnNiP ϭ 1199.1 Hz, JSnP ϭ 239.1 Hz). Ϫ 13C NMR
2
2
(62.90 MHz, C6D6): δ ϭ 6.2 (dd, SnCH2, JPCC ϭ 31.1 Hz,
3JPNiSnC ϭ 11.0 Hz), 12.9 (d, PCH3, JPC ϭ 22.6 Hz), 32.9 (dd,
1
1
3
PCH2, JPC ϭ 33.0 Hz, JPNiPC ϭ 9.2 Hz, 126.7Ϫ146.8 (C6H5). Ϫ
Reaction of Ni(COD)2 with Ph2PCH2CH2SnPh2Me: A solution
of 1.08g (2.16 mmol) of Ph2PCH2CH2SnPh2Me in 5 ml of THF
was added to 297 mg (1.08 mmol) Ni(COD)2, dissolved in 20 ml
of THF. The deep red solution was stirred for 4 h while a small
amount of gas was evolved. Removal of all volatiles in vacuo left
a brown oil. Ϫ 31P NMR (101.250 MHz, C6D6): δ ϭ 57.9 (d,
1H NMR (250.130 MHz, C6D6): δ ϭ 0.73 (d, PCH3, JPCH ϭ 6.1
2
Hz), 1.17Ϫ1.33 (m, SnCH2), 2.59Ϫ2.78 (m, PCH2), 6.90Ϫ7.73
(m, C6H5).
Preparation of (Cy3P)Ni(Ph)[Ph2PCH2CH2SnPh2(NiϪSn)]
( ): A solution of 258 mg (0.92 mmol) of PCy3 and 518 mg (0.92
mmol) of Ph2PCH2CH2SnPh3 in 5 ml benzene was added to a sus-
pension of 252 mg (0.92 mmol) of Ni(COD)2 in 15 ml of heptane.
A red-brown solution formed almost immediately. After additional
stirring for 4 h, during which the color slightly lightened, the solu-
tion was filtered through glass wool. From the resulting deep red
solution all volatiles were removed in vacuo. The remaining golden-
red oil was chromatographed on silica gel with Et2O/petroleum
ether (1:50). The complex was eluted as a deep yellow zone. After
removal of the solvent, 620 mg (75%) of was obtained as a brown-
yellow powder. M.p. 69°C (dec.). Ϫ C50H62P2NiSn (902.3): calcd.
C 66.6, H 6.93; found C 65.9, H 6.81. Ϫ 31P NMR (101.250 MHz,
2
2JPNiP ϭ 6.1 Hz, J117/119SnP ϭ 213 Hz), 25.3 (d, JPNiP ϭ 6.1 Hz).
Preparation of (Ph3SnCH2CH2Ph2P)Pt[PPh2CH2CH2SnPh2-
(PtϪSn)](Ph) ( ): A solution of 193 mg (0.35 mmol) of
Ph2PCH2CH2SnPh3 in 3 ml of benzene was added to a solution of
117 mg (0.17 mmol) of (Ph3P)2Pt(C2H4) in 12 ml of benzene. An
immediate color change to bright yellow and gas evolution oc-
curred. The solution was stirred for additional 10 h at room tem-
perature, resulting in a pale yellow solution. A yellow oil remained
after removal of all volatiles in vacuo. Complex was obtained as
a pale yellow powder on washing the oil three times with 5 ml of
petroleum ether each at 0°C and drying in vacuo. Yield 128 mg
(57%). M.p. 95°C (dec.). Ϫ C64H58P2PtSn2 (1321.6): calcd. C 58.2,
H 4.42; found C 57.9, H 4.30. Ϫ 31P NMR (101.250 MHz, C6D6):
2
C6D6): δ ϭ 51.9 (d, JPNiP ϭ 8.6 Hz, J119SnP ϭ 222.2 Hz,
2
2
J117SnP ϭ 206 Hz), 22.5 (d, JPNiP ϭ 8.6 Hz, J119SnNiP ϭ 1036.3
Hz, 2J117SnNiP ϭ 991.2 Hz). Ϫ 119Sn NMR (93.276 Hz, C6D6): δ ϭ
2
1
δ ϭ 51.8 (d, JPPtP ϭ 11.0 Hz, JPtP ϭ 2020.2 Hz, JSnP ϭ 115.0
16.7 (dd, J119SnNiP ϭ 1036.3 Hz, J119SnNiP ϭ 218.7 Hz). Ϫ 13C
2
2
2
1
2
Hz), 24.1 (d, JPPtP ϭ 11.0 Hz, JPtP ϭ 2184.9 Hz, J119SnPtP
ϭ
2
1712.6 Hz, J117SnPtP ϭ 1635.7 Hz, JSnCCP ϭ 179.4 Hz). Ϫ 119Sn
2
3
NMR (62.90 MHz, C6D6): δ ϭ 5.2 (dd, SnCH2, JPCC ϭ 29.6 Hz,
3JPNiSnC ϭ 12.2 Hz), 32.7 (dd, PCH2 JPC ϭ 31.4 Hz, JPNiPC
ϭ
1
2
2
NMR (93.276 MHz, C6D6): δ ϭ 97.2 (dd, J119SnPtP ϭ 1711.5 Hz,
1
J119SnP ϭ 117.0 Hz), Ϫ97.5 (d, J119SnCCP ϭ 180.6 Hz). Ϫ 13C
3
6.9 Hz), 34.7 (d, JPC ϭ 11.6 Hz), 30.7 (s), 27.8 (d, JPC ϭ 9.4
Hz), 26.8 (s), signals of PCy3, 121.1Ϫ156.2 (C6H5), 155.6 (dd, NiC,
2
NMR (62.90 MHz, C6D6): δ ϭ 4.1 (d, JPCC ϭ 7.5 Hz, SnCH2),
2JPNiC ϭ 59.2 Hz, JPNiC ϭ 7.9 Hz). Ϫ H NMR (250.130 MHz,
C6D6): δ ϭ 0.93Ϫ0.98 (m, SnCH2, 2 H), 1.15 (s, br.) 1.51Ϫ1.80
(m) (cyclohexyl, 33 H), 2.65Ϫ2.87 (m, PCH2, 2 H), 6.95Ϫ7.10 (m,
NiC6H5), 7.07Ϫ7.79 (m, C6H5).
2
1
2
3
5.2 (dd, JPCC ϭ 23.6 Hz, JPPtSnC ϭ 12.0 Hz, SnCH2), 24.4 (d,
1JPC ϭ 20.8 Hz, PCH2) 36.6 (dd, JPC ϭ 37.5 Hz, JPC ϭ 8.8 Hz,
1
PCH2), 124.3Ϫ156.3 (C6H5, no assignment was possible due to dif-
ferent phenyl groups and Pt satellites). Ϫ 1H NMR (250.130 MHz,
C6D6): δ ϭ 0.80Ϫ1.28 (m, overlapping, 4 H, SnCH2), 2.15Ϫ2.32
(m, 2 H, PCH2), 2.45Ϫ2.68 (m, 2 H, PCH2), 6.78Ϫ7.73 (m, C6H5).
Thermal Reaction of : An amount of 350 mg of the crude com-
plex was dissolved in 20 ml of toluene and heated in a sealed
Schlenk tube for 9 h to 70°C. Then the solvent was removed in
vacuo. The oily yellowish brown residue was analyzed by 31P- and
119Sn-NMR spectroscopy, which showed partial formation of
Ni[Ph2PCH2CH2SnPh2(NiϪSn)]2 ( ) and some decomposition.
The reaction products could not be separated. The NMR data are
given in the next paragraph.
Preparation of (Me3SnCH2CH2Ph2P)Pt[PPh2CH2CH2SnMe2-
(PtϪSn)](Me) ( ). Ϫ Method a: A solution of 128 mg (0.17
mmol) of (Ph3P)2Pt(C2H4) in 10 ml of benzene was treated with
130 mg (0.35 mmol) of Ph2PCH2CH2SnMe3 in 4 ml of benzene at
room temperature for 12 h. After removal of the solvent in vacuo,
an orange oil remained. The product was crystallized from a con-
centrated benzene solution by heptane diffusion as pale yellow
crystals in 55% yield (89 mg). M.p. 132°C. Ϫ C34H46P2PtSn2
(949.2): calcd. C 43.0, H 4.88, found C 43.4, H 4.65.
Preparation of Ni[(Ph2PCH2CH2SnPh2(NiϪSn)]2 ( ) from
Ph2PCH2CH2SnPh2H: A solution of 400 mg (0.82 mmol) of
Ph2PCH2CH2SnPh2H in 6 ml of THF was added to a yellow solu-
tion of 108 mg (0.41 mmol) of Ni(COD)2 in 10 ml of THF. The
reaction mixture immediately turned red, and a gas was evolved.
Method b: To a beige solution of 131 mg (0.32 mmol) of
Pt(COD)2 in
3
ml of benzene, 242 mg (0.64 mmol) of
902
Eur. J. Inorg. Chem. , 897Ϫ903

Transition Metal Stannyl Complexes, 12
FULL PAPER
¯
Ph2PCH2CH2SnMe3 was added, resulting in a color change to yel-
X-ray Structure Analysis of : Triclinic, space group P1, a ϭ
low-brown. On stirring for 16 h, the color of the reaction mixture 1241.42(1), b ϭ 1280.91(2), c ϭ 1578.98(3) pm, α ϭ 66.396(1), β ϭ
became lighter. All volatiles were removed in vacuo after filtration
69.796(1), γ ϭ 66.749(1)°, V ϭ 2060.91·106(3) pm3, dcalcd. ϭ 1.655
through glass wool, and the remaining slightly oily solid was g cmϪ3 for Z ϭ 2. F(000) ϭ 1000, µ(Mo-Kα) ϭ 4.690 mmϪ1, λ ϭ
washed twice at 0°C with 3 ml of pentane each. After drying,
was obtained as a beige powder (210 mg, 69%).
71.073 pm, T ϭ 302 K, crystal size ϭ 0.5 ϫ 0.4 ϫ 0.25 mm. A
crystal was sealed in a glass capillary and mounted on a Siemens
SMART diffractometer with a CCD area detector. A hemisphere
of data was collected by a combination of three sets of exposures
(17343 reflections). Each set had a different ␾ angle for the crystal,
and each exposure took 15 s and covered 0.3° in ω (2.9° Յ 2Θ Յ
60.1°). The crystal-to-detector distance was 3.85 cm. The data were
corrected for polarization and Lorentz effects, and an empirical
absorption correction (SADABS) was applied (11897 unique reflec-
tions). The structure was solved by the Patterson method
(SHELS86). Refinement was carried out with the full-matrix least-
squares method based on F2 (SHELXL93) with anisotropic ther-
mal parameters for all non-hydrogen atoms. Hydrogen atoms were
inserted in calculated positions and refined riding with the corre-
sponding atom. Refinement converged at R1 ϭ 0.0595 [for 1847
reflections with I > 2σ(I)], wR2 ϭ 0.1344 {w ϭ [σ2(Fo)2 ϩ (0.0·x
2
31P NMR (101.250 MHz, C6D6): δ ϭ 55.9 (d, JPPtP ϭ 7.3 Hz,
2
1JPtP ϭ 2152.2 Hz, JSnP ϭ 108.6 Hz), 27.9 (d, JPPtP ϭ 7.3 Hz,
2
1JPtP ϭ 2065.5 Hz, J119SnPtP ϭ 1726.2 Hz, 2J117SnPtP ϭ 1696.8 Hz,
3JSnCCP ϭ 213.6 Hz). Ϫ 119Sn NMR (93.276 MHz, C6D6): δ ϭ
2
147.2 (dd, J119SnPtP ϭ 1732.1 Hz, J119SnP ϭ 111.9 Hz), Ϫ29.5 (d,
3J119SnCCP ϭ 218.7 Hz). Ϫ 13C NMR (62.90 MHz, [D8]toluene):
δ ϭ Ϫ11.7 (dd, trans-2JPPtC ϭ 82.9 Hz, cis-2JPPtC ϭ 7.6 Hz,
3
2
PtCH3), Ϫ9.6 (s, SnCH3), Ϫ6.5 (d, JPPtSnC ϭ 8.2 Hz, JPtSnC
ϭ
78.5 Hz, SnCH3), 5.8 (s, br., SnCH2), 6.1 (d, JPC ϭ 13.1 Hz,
SnCH2), 25.4 (d, br., 1JPC ϭ 12.0 Hz, PCH2), 39.4 (dd, 1JPC ϭ 39.2
Hz, JPC ϭ 8.7 Hz, PCH2). Ϫ 1H NMR (250.130 MHz, [D8]tol-
2
uene): δ ϭ Ϫ0.11 (s, JSnCH ϭ 51.3 Hz, 9 H, SnCH3), 0.55 (s,
2JSnCH ϭ 41.5 Hz, SnCH3, 6H), 0.65 (d, 3JPPtCH ϭ 6.1 Hz, PtCH3),
0.71Ϫ 0.95 (m, SnCH2), 1.44Ϫ1.52 (m, 2J117/119SnCH ഠ 59 Hz, 2 H,
SnCH2), 2.03Ϫ2.12 (m, PCH2), 2.48Ϫ2.61 (m, PCH2, 2 H),
6.98Ϫ7.75 (m, C6H5).
P)2 ϩ x·P]Ϫ1, where P ϭ (Fo2 ϩ 2Fc )/3}; final GOF ϭ 0.511. The
2
¯
Ϫ3
final difference map showed no peak larger than ϩ2.008 e
and
¯
Ϫ3 [21]
no hole larger than Ϫ1.243 e
.
Preparation of (Bu3SnCH2CH2Ph2P)Pt[PPh2CH2CH2SnBu2-
(PtϪSn)](Bu) ( ): The reaction was carried out in benzene as
described for , using 160 mg (0.22 mmol) of (Ph3P)2Pt(C2H4) and
227 mg (0.45 mmol) of Ph2PCH2CH2SnBu3. Removal of all vol-
atiles in vacuo resulted in a yellow oil (consisting of in about 90%
yield according to the 31P-NMR spectrum). By washing the oil
twice with 8 ml of pentane each and drying in vacuo, a yellow
powder was obtained that contained and only traces of impurities
according to the 31P-NMR spectrum. Ϫ 31P NMR (101.25 MHz,
[1]
Part 11: U. Schubert, S. Grubert, Organometallics
, 15,
4707.
[2]
[3]
[4]
[5]
U. Schubert, Angew. Chem.
, 106, 435; Angew. Chem. Int.
Ed. Engl.
G. Butler , C. Eaborn, A. J. Pidcock, Organomet. Chem.
181, 47.
T. A. K.Al-Allaf, C. Eaborn, K. Kundu, A. J. Pidcock, J. Chem.
, 33, 419.
,
Soc., Chem. Commun.
, 55.
2
1
G. Butler, C. Eaborn, A. J. Pidcock, Organomet. Chem.
185, 367.
,
C6D6): δ ϭ 53.2 (d, JPPtP ϭ 9.3 Hz, JPtP ϭ 1899.5 Hz,
2
1
J117/119SnP ϭ 110.2 Hz), 27.9 (d, JPPtP ϭ 9.3 Hz, JPtP ϭ 2097.2
[6]
[7]
C. Eaborn, K. Kundu, A. Pidcock, J. Chem. Soc.
, 1223.
2
2
3
Hz, J119SnPtP ϭ 1671.2 Hz, J117SnPtP ϭ 1596.7 Hz, J119SnCCP
ϭ
B. Cetinkaya, M. F. Lappert, J. McMeeking, D. E. Palmers, J.
185.6 Hz, J117SnCCP ϭ 178.2 Hz). Ϫ 119Sn NMR (93.276 MHz,
3
Chem. Soc., Dalton Trans.
, 1202.
[8]
[9]
C6D6): δ ϭ 175.8 (dd, 2J119SnPtP ϭ 1673.4 Hz, J119SnP ϭ 111.9 Hz),
H. Werner, O. Gevert, P. Haquette, Organometallics
, 16,
803.
Ϫ4.8 (d, JPCC119Sn ϭ 185.7 Hz). Ϫ 1H NMR (250.130 MHz,
3
M. J. Auburn, R. D. Holmes Smith, S. R. Stobart, J. Am. Chem.
C6D6): δ ϭ 0.75Ϫ1.96 (complex overlapping multiplets of butyl
groups and SnCH2), 2.20Ϫ2.51 (m, PCH2), 2.65Ϫ2.80 (m, PCH2)
6.99Ϫ7.90 (m, C6H5).
Soc.
, 106, 1314.
[10]
[11]
C. Müller, U. Schubert, Chem. Ber.
, 124, 2181.
U. Schubert, S. Grubert, U. Schulz, S. Mock, Organometallics
, 11, 3165.
[12]
[13]
Preparation
of
(PhMe2SnCH2CH2Ph2P)Pt[PPh2CH2-
B. P. Buffin, M. J. Poss, A. M. Arif, T. G. Richmond, Inorg.
CH2SnMe2(PtϪSn)](Ph) ( ): An amount of 123 mg (0.16 mmol)
of (Ph3P)2Pt(C2H4) and 144 mg (0.16 mmol) of
Ph2PCH2CH2SnMe2Ph was treated as described above. After re-
moval of all volatiles, the yellow oil was analyzed by multinuclear
NMR which indicated the almost quantitative formation of ac-
cording to 31P NMR. Ϫ 31P NMR (101.250 MHz, C6D6): δ ϭ 52.8
Chem.
, 32, 3805.
H. Gilges, U. Schubert, J. Organomet. Chem.
Murikami, T. Yoshida, Y. Ito, Organometallics
M. Murikami, T.Yoshida, Y. Ito, Chem. Lett.
, 548, 57; M.
, 13, 2900;
, 13.
[14]
[15]
[16]
H. Weichmann, J. Organomet. Chem.
, 238, C49.
P. E. Garrou, P. E. Chem. Rev. , 81, 229.
E. Carmona, E. Gutierrez-Puebla, J. M. Marin, A. Monge, M.
Paneque, M. L. Poveda, C. Ruiz, J. Am. Chem. Soc.
111, 2883.
,
2
1
(d, JPPtP ϭ 11.0 Hz, JPtP ϭ 2116.0 Hz, J117/119SnP ϭ 104.1 Hz),
2
1
2
[17]
[18]
24.4 (d, JPPtP ϭ 11.0 Hz, JPtP ϭ 2046.2 Hz, J119SnPtP ϭ 1572,3
H. Azizian, K. R. Dixon, C. Eaborn, A. Pidcock, N. M. Shuaib,
Hz, J117SnPtP ϭ 1503.7 Hz, J119/117SnCCP ϭ 200.0 Hz). Ϫ 119Sn
J. Vinaixa, J. Chem. Soc.
, 1020.
2
3
NMR (93.276 MHz, C6D6): δ ϭ 161.2 (dd 2J119SnPtP ϭ 1572.9 Hz,
Comprehensive Organometallic Chemistry, vol. 9 (Eds.: E. W.
Abel, F. G. A. Stone, G. Wilkinson), Pergamon Press, Oxford,
, p. 454.
J
119SnP ϭ 104.4 Hz) Ϫ25.5 (d, 3J119SnCCP ϭ 208.0 Hz). Ϫ 13C NMR
[19]
[20]
[21]
(62.90 MHz, C6D6):
δ ϭ Ϫ11.1 [s, Sn(CH3)2Ph], Ϫ7.4 [d,
H. C. Clark, G. Ferguson, M. J. Hampden-Smith, H. Ruegger,
2
2
3JPPtSnC ϭ 6.9 Hz, JPtSnC ϭ 74.9 Hz, Sn(CH3)2], 3.7 (d, JPCC
ϭ
B. L. Ruhl, Can. J. Chem.
, 66, 3120.
7.4 Hz, SnCH2), 6.6 (d, 2JPCC ϭ 16.2, SnCH2), 25.4 (d, br., 1JPC ϭ
18.5 Hz, PCH2) 37.6 (dd, JPC ϭ 38.4 Hz, JPC ϭ 8.8 Hz, PCH2),
H. Weichmann, G. Quell, A. Tzschach, Z. Anorg. Allg. Chem.
, 503, 7.
1
Crystallographic data (excluding structure factors) for the struc-
ture reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union
Road, Cambridge C82 1EZ, UK [fax: int. code ϩ(1223)336-
033; e-mail: deposit@ccdc.cam.ac.uk] quoting the depository
number CCDC-101015.
121.9Ϫ156.6 (C6H5, no assignment possible due to different phenyl
groups and Pt satellites). Ϫ 1H NMR (250.13 MHz, C6D6): δ ϭ
3
0.04 (s, 2JSnCH ϭ 53.0 Hz, 6 H, SnCH3), 0.36 (s, br, JPtSnCH ϭ 8.1
Hz, 6 H, SnCH3), 0.58Ϫ0.73 (m, SnCH2), 1.05Ϫ1.19 (m, SnCH2),
2.09Ϫ2.21 (m, 2 H, PCH2), 2.53Ϫ2.67 (m, 2 H, PCH2), 6.87Ϫ6.98
(m, 5 H, PtC6H5), 7.10Ϫ7.86 (m, C6H5).
[98011]
Eur. J. Inorg. Chem.
, 897Ϫ903
903