Synthesis of novel trialkyl(trichlorostannyl)platinum(IV) complexes through SnCl2 insertion into the Pt-Cl bond

Article abstract of DOI:10.1021/om0207414

Reaction of SnCl₂ with the trialkylplatinum(IV) complexes [PtClMe₂(R)(bipy)] (1) resulted in the formation of the novel trialkyl(trichlorostannyl)platinum(IV) complexes [PtMe₂(R)(SnCl₃)(bipy)] (R = allyl (2a), Me (2b), Bz (2c)). The solid-state molecular structure of fac-[PtMe₃(SnCl₃)(bipy)] revealed a direct PtSn bond (2.6497(2) A) and three almost identical PtMe bond lengths (2.065(5) and 2.068(8) A both cis and 2.069(5) A trans to SnCl₃. The presence of platinum satellites (¹J_SnPt = 3267-4260 Hz) in the ¹¹⁹Sn NMR spectra of complexes 2 indicates that the direct platinumtin bond is maintained in solution. Addition of 1 equiv of PPh₃ to complexes 2 resulted in the formation of the trichlorostannate complexes fac-[PtMe₂(R)(bipy)(PPh₃)][SnCl₃] (3). The absence of platinum satellites on the ¹¹⁹Sn NMR signal of 3 confirmed the ionic character of these complexes in solution.

Full text of DOI:10.1021/om0207414

1156
Organometallics 2003, 22, 1156-1159
Syn th esis of Novel
Tr ia lk yl(tr ich lor osta n n yl)p la tin u m (IV) Com p lexes
th r ou gh Sn Cl2 In ser tion in to th e P t-Cl Bon d
Sander H. L. Thoonen,† Martin Lutz,‡ Anthony L. Spek,‡
Berth-J an Deelman,*,†,§ and Gerard van Koten†
Debye Institute, Department of Metal-Mediated Synthesis, and Bijvoet Center for Biomolecular
Research, Department of Crystal and Structural Chemistry, Utrecht University, Padualaan 8,
3584 CH, Utrecht, The Netherlands, and ATOFINA Vlissingen BV, PO Box 70,
4380 AB Vlissingen, The Netherlands
Received September 9, 2002
Summary: Reaction of SnCl2 with the trialkylplatin-
um(IV) complexes [PtClMe2(R)(bipy)] (1) resulted in the
formation of the novel trialkyl(trichlorostannyl)plat-
inum(IV) complexes [PtMe2(R)(SnCl3)(bipy)] (R ) allyl
(2a ), Me (2b), Bz (2c)). The solid-state molecular struc-
ture of fac-[PtMe3(SnCl3)(bipy)] revealed a direct Pt-
Sn bond (2.6497(2) Å) and three almost identical Pt-
Me bond lengths (2.065(5) and 2.068(8) Å both cis and
2.069(5) Å trans to SnCl3). The presence of platinum
satellites (1J SnPt ) 3267-4260 Hz) in the 119Sn NMR
spectra of complexes 2 indicates that the direct platinum-
tin bond is maintained in solution. Addition of 1 equiv
of PPh3 to complexes 2 resulted in the formation of the
trichlorostannate complexes fac-[PtMe2(R)(bipy)(PPh3)]-
[SnCl3] (3). The absence of platinum satellites on the
119Sn NMR signal of 3 confirmed the ionic character of
these complexes in solution.
It was Kuyper who reported the first examples of
platinum(IV) trichlorostannyl complexes, i.e., [PtClMe2-
(SnCl3)(N-N)] (N-N ) 2,2′-bipyridine, 2,9-dimethyl-4,7-
diphenyl-1,10-phenanthroline),4 which were obtained
from oxidative addition of SnCl4 on [PtMe2(N-N)]. [Pt-
ClMe2(SnCl3)(paen-me2)]5 (paen-me2 ) N-(â-(dimethyl-
amino)ethyl)pyridinealdimine) and [PtClMe2(SnMen-
Cl3-n)(bipy)] (n ) 1-3)4 can be prepared in a similar
way. Other Pt(IV)-stannyl complexes obtained by reac-
tion of organoplatinum(II) complexes with tin(IV) re-
agents are [Pt(SnMe3)(Ph)(H)2(PEt3)2],6 [PtIMe2(SnMe3)-
(But bpy)],5 [PtMe2(SnMe3)((pz)3BH)]7 ((pz)3BH ) tris-
2
(pyrazol-1-yl)borate),ionic[PtMe2(Me2SnCl)(But bpy)]+[Y]-,
2
and [PtClMe2(SnPh3-xClx)(But bpy)]8 (Y ) BF4, PF6; X
2
) 1-3; But bpy ) 4,4′-di-tert-butyl-2,2′-bipyridine).9 In
2
all these Pt(IV) stannyl complexes, the stannyl substi-
tuent was introduced by oxidative addition of a tin(IV)
species to a Pt(II) complex. Recently, Puddephatt et al.
reported on the reductive elimination of Me3SnX and
Me4Sn from [PtXMe2(SnMe3)(diimine)] (X ) Cl, Br, I)
complexes, underlining the intermediacy of Pt(IV)-
stannyl complexes in Sn-C bond formation.10
In tr od u ction
Heterobimetallic complexes of tin and group 10 metals
have been known for several decades.1 M(II) trihalo-
stannyl complexes can be prepared via SnX2 insertion
into the M-X bond (M ) Pt, Pd; X ) Cl, Br) and are
excellent catalysts for hydrogenation of olefins and al-
kynes2 as well as for the hydroformylation of alkenes.3
In these catalytic reactions, the [SnX3]- anion serves
as a weakly coordinating anionic ligand, which allows
the facile creation of a vacant coordination site at the
metal center.
Here we report on the novel trialkyl(trichlorostannyl)-
platinum(IV) complexes [PtMe2(R)(SnCl3)(bipy)] (2) and
related stannate complexes [PtMe2(R)(PPh3)(bipy)][Sn-
Cl3] (3), which were synthesized through the unprece-
dented insertion of SnCl2 into the PtIV-Cl bond. As
these alkyl(trichlorostannyl)platinum complexes show
a tendency to undergo reductive Sn-C bond formation,
they are relevant for the oxidative alkylation of stan-
nous halides. This aspect will be the subject of a
subsequent paper.
* To whom correspondence should be addressed at ATOFINA
Vlissingen BV. Fax: +31 113 612984. E-mail: Berth-J an.Deelman@
atofina.com.
† Debye Institute, Department of Metal-Mediated Synthesis, Utrecht
University.
‡ Bijvoet Center for Biomolecular Research, Department of Crystal
and Structural Chemistry, Utrecht University.
Resu lts a n d Discu ssion
§ ATOFINA Vlissingen BV.
Syn th esis of P tMe2(R)(Sn Cl3)(bip y) (2). Reaction
of complexes [PtClMe2(R)(bipy)]11a-c (1) with SnCl2
(1) (a) Review: Holt, M. S.; Wilson, W. L.; Nelson, J . H. Chem. Rev.
1989, 89, 11-49. (b) Kolla´r, L.; Gladiali, S.; Tenorio, M. J .; Weissen-
steiner, W. J . Cluster Sci. 1998, 9, 3, 321. (c) Naili, S.; Carpentier,
J .-F.; Agbossou, F.; Mortreux, A. New J . Chem. 1997, 21, 919. (d)
Ammann, C.; Pregosin, P. S. Inorg. Chim. Acta 1989, 155, 217. (e)
Gianotti, M.; Musco, A.; Sisti, M.; Grassi, M.; Gatti, G. Inorg. Chim.
Acta 1987, 133, 255. (f) Albinati, A.; Moriyama, H.; Ru¨egger, H.;
Pregosin, P. S.; Togni, A. Inorg. Chem. 1985, 24, 4430. (g) Goel, A. B.;
Goel, S. Inorg. Chim. Acta 1983, 77, L53. (h) Grossel, M. C.; Moulding,
R. P.; Seddon, K. R. Inorg. Chim. Acta 1982, 64, L275. (i) Mason, R.;
Whimp, P. O. J . Chem. Soc. A 1969, 2709.
(2) Deibele, C.; Permin, A. B.; Petrosyan, V. S.; Bargon, J . Eur. J .
Inorg. Chem. 1998, 1915.
(3) (a) Scrivanti, A.; Beghetto, V.; Bastianini, A.; Matteoli, U.;
Menchi, G. Organometallics 1996, 15, 4687. (b) Gladiali, S.; Alberico,
E.; Pulacchini, S.; Kolla`r, L. J . Mol. Catal. 1999, 143, 155. (c) To´th, I.;
Elsevier, C. J .; de Vries, J . G.; Bakos, J .; Smeets, W. J . J .; Spek, A. L.
J . Organomet. Chem. 1997, 540, 15.
(4) Kuyper, J . Inorg. Chem. 1977, 16, 2171.
(5) Levy, C. J .; Vittal, J .; Puddephatt, R. J . Organometallics 1996,
15, 2108.
(6) Arnold, D. P.; Bennett, M. A. Inorg. Chem. 1984, 23, 2110.
(7) (a) Canty, A. J .; J in, H.; Skelton, B. W.; White, A. H. Aust. J .
Chem. 1999, 52, 417. (b) Canty, A. J .; J in, H. J . Organomet. Chem.
1998, 565, 135.
(8) J anzen, M. C.; J ennings, M. C.; Puddephatt, R. J . Organome-
tallics 2001, 20, 4100.
(9) Levy, C. J .; Vittal, J . J .; Puddephatt, R. J . Organometallics 1996,
15, 35.
(10) (a) Levy, J . C.; Puddephatt, R. J . Organometallics 1997, 16,
4115. (b) Levy, C. J .; Puddephatt, R. J . J . Am. Chem. Soc. 1997, 119,
10127. (c) Levy, C. J .; Puddephatt, R. J . J . Chem. Soc., Chem. Commun.
1995, 2115.
10.1021/om0207414 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 01/31/2003

Notes
Organometallics, Vol. 22, No. 5, 2003 1157
Ta ble 1. 1H NMR Da ta for [P tClMe2R(bip y)] (1) a n d th e Novel P t(IV) Com p lexes [P tMe2R(Sn Cl3)(bip y)] (2)
a n d [P tClMe2R(P P h 3)(bip y)][Sn Cl3] (3)a
R-H of R
2J HPt 3J HP 3J HSn
Pt-Me (trans to bipy)
2J HPt 3J HP 3J HSn
com-
plex
R
bipy ligand
δ
δ
other
1a b
1bc
1cd
2a
allyl 7.58 (t, 2H), 8.06 (t, 2H),
8.18 (d, 2H), 8.88 (d, 2H)
2.13 (d,
2H)
0.47 (s,
3H)
2.81 (s,
2H)
2.25 (d,
2H)
0.71 (s,
3H)
2.88 (s,
2H)
95
82
94
1.37 (s,
6H)
1.36 (s,
6H)
1.47 (s,
6H)
70
69
70
69
69
69
4.15-4.36 (m, 2H), 5.00-5.23
3
(ps sext, 1H, J HH ) 9.2 Hz)
Me
7.61 (t, 2H), 8.04 (t, 2H),
8.24 (d, 2H), 8.91 (d, 2H)
7.45 (t, 2H), 7.86-7.00
(m, 4H), 8.71 (d, 2H)
3
Bz
6.27-6.34 (d, 2H, J HH
)
7.0 Hz), 6.53-6.67 (m, 3H)
4.17-4.32 (m, 2H), 5.00 (ps
sext, 1H, J HH ) 8.8 Hz)
allyl 7.72 (t, 2H), 8.13 (t, 2H),
84
68
82
18.0 1.30 (s,
f
3
8.32 (d, 2H), 8.84 (d, 2H)
6H)
2b
Me
Bz
7.74 (t, 2H), 8.17 (t, 2H),
8.34 (d, 2H), 8.93 (d, 2H)
7.55 (d, 2H), 8.01 (m,
4H), 8.70 (d, 2H)
6.0 1.34 (s,
6H)
4.5
3
2c
19.2 1.41 (s,
f
6.20 (d, 2H, J HH ) 7.0 Hz),
3
6H)
6.61 (t, 2H, J HH ) 7.8),
3
6.71 (t, 1H, J HH ) 7.2 Hz)
3a
allyl 8.00 (d, 2H), 8.27 (t,
2H), 8.92 (d, 2H)e
1.98 (d,
2H)
75
8.8
1.30 (d,
6H)
67
10.2
4.16-4.23 (m, 2H), 4.81-5.03
3
(ps sext, 1H, J HH ) 6.2 Hz),
3
6.98 (t, 6H, J HH ) 9.4 Hz),
7.21-7.68 (m, 11 H)
3
3b
3c
Me
Bz
8.16 (d, 2H), 8.31 (t,
2H), 8.86 (d, 2H)e
7.88 (d, 2H), 8.17 (t,
2H), 8.60 (d, 2H)e
0.48 (d,
3H)
2.65 (d,
2H)
59
73
7.2
1.32 (d,
6H)
1.40 (d,
6H)
67
67
7.6
6.8
6.93 (t, 6H, J HH ) 8.2 Hz),
7.20-7.46 (m, 11H)
3
12.0
6.15 (d, 2H, J HH ) 8.1 Hz),
3
6.59 (m, 3H), 6.91 (t, 6H, J HH
)
8.0 Hz), 7.18-7.37 (m, 11H)
a
b
d
Recorded at 200.13 MHz in CDCl3 at ambient temperature. See ref 11c. c See ref 11b. See ref 11a. e Overlap of bipy resonances
with PPh3 resonances. f Not observed.
Ta ble 2. 31P {1H} a n d 119Sn {1H} NMR Da ta for th e
afforded the novel platinum(IV) trichlorostannyl com-
plexes [PtMe2(R)(SnCl3)(bipy)] (R ) allyl (2a ), Me (2b),
Bz (2c)) in high yield (eq 1).
Novel P t(IV) Com p lexes [P tMe2R(Sn Cl3)(bip y)] (2)
a n d [P tClMe2R(P P h 3)(bip y)][Sn Cl3] (3)a
119Sn
1J SnPt (Hz)
31P
compd
δ (ppm)
δ (ppm)
1J PPt (Hz)
2a b
2bb
2cb
3a
3b
3c
20.6
-6.1
3267
4260
3415
17.2
-48.9
-49.6
-46.3
-0.69
-2.40
-1.23
972
984
967
a
Recorded at 81.02 MHz (31P) and 74.63 MHz (119Sn) in CDCl3
b
at ambient temperature. Recorded in CH2Cl2 at ambient tem-
perature.
Complexes 2 are yellow solids, which are soluble in
CH2Cl2, CHCl3, THF, and acetone. The identity of com-
1
3415 Hz, respectively) (Table 2). The observation of 195Pt
satellites is direct proof for the presence of a platinum-
tin bond in solutions of complexes 2.
plexes 2 was established by elemental analysis and H
1
and 119Sn NMR spectroscopy. The H NMR spectra of
complexes 2 recorded in CDCl3 (Table 1) show one signal
for the two methyl ligands trans to the bipy ligand and
four signals for the bipy ligand itself, pointing to a
complex with the R and SnCl3 substituents in trans
positions. The resonances of the two PtMe groups trans
to the bipy ligand show platinum satellites of 69 Hz,
which is a typical value for a PtIVMe resonance.5-9 In
the case of 2a and 2c, the 3J HSn sattelite signals flanking
the PtMe resonance trans to the bipy ligand are not
observed. A small coupling of 3J HSn ) 4.5 Hz is seen for
The magnitude of the platinum-tin coupling con-
stants of 2 are at the low end of the range (2 500-35 000
Hz) found in the literature,12 indicating a weak Pt-Sn
interaction. Unfortunately, no reference data for Pt-
SnCl3 complexes with bidentate nitrogen ligands are
available. For complexes of the type trans-[Pt(SnCl3)-
1
(Y)(PEt3)2], J PtSn values of 6620 and 5775 Hz were
found for Y ) Me, CH2Ph, respectively.13 The magnitude
of these values is comparable to those found for 2.
Dissociation of the SnCl3 ligand from the Pt center
to give [PtMe2R(bipy)][SnCl3] can be excluded, even in
coordinating solvents such as acetone; 1H NMR spectra
of 2b recorded in acetone-d6 showed platinum and tin
satellites for the PtMe resonance in a position trans to
the SnCl3 substituent, indicating the covalent Pt-Sn
bond is retained in solution.
3
2b. This value is in agreement with the J HSn values
reported for other platinum(IV)-stannyl complexes.5
The methylene proton resonances of R are shifted
downfield by ca. 0.09-0.24 ppm relative to 1, as a result
of the introduction of the strongly electron-withdrawing
SnCl3 substituent. Furthermore, a decrease of the coup-
2
ling constant J HPt for these methylene protons by 10
Hz was found. For all three complexes we observed also
3J HSn coupling for the methylene protons (18.0 (2a ), 6.0
(2b), and 19.2 Hz (2c), respectively). 119Sn NMR spectra
of complexes 2 recorded in CH2Cl2 solution showed one
singlet (δ +20.6 (2a ), -6.1 (2b), and +17.6 (2c), respec-
tively) with 195Pt satellites (1J SnPt ) 3267, 4260, and
Molecu la r Str u ctu r e of fa c-[P tMe3(Sn Cl3)(bip y)]
(2b). The structure of 2b in the solid state was solved
by a single-crystal X-ray diffraction study (Figure 1).
Selected bond distances and bond angles are listed in
Table 3.
(12) (a) Ostoja Starzewski, K. H. A.; Pregosin, P. S.; Ru¨egger, H.
Helv. Chim. Acta 1982, 65, 785. (b) Kretschmer, M.; Pregosin, P. S.;
Ru¨egger, H. J . Organomet. Chem. 1983, 241, 87.
(13) Albinati, A.; von Gunten, U.; Pregosin, P. S.; Ruegg, H. J . J .
Organomet. Chem. 1985, 295, 239.
(11) (a) Crespo, M.; Puddephatt, R. J . Organometallics 1987, 6, 2548.
(b) Prepared analogously to fac-[PtClMe3(Bu2bpy)] according to: Hill,
G. S.; Vittal, J . J .; Puddephatt, R. J . Organometallics 1997, 16, 1209.
(c) Kuyper, J . J . Inorg. Chem. 1978, 17, 77.

1158 Organometallics, Vol. 22, No. 5, 2003
Notes
than the other two Pt-Me bonds. However, since all
Pt-Me distances found were nearly of the same length,
we can only conclude that there is a low trans influence
of the stannyl group, presumably caused by the rela-
tively long Pt-Sn distance (2.6497(3) Å). As expected,
the PtIV-Sn distance is longer than in Pt(II) com-
pounds14 but also significantly longer than in other
known Pt(IV) compounds (2.54-2.57 Å).5,7a,9 We assume
that this long bond length is a consequence of the
electron-withdrawing effect of the three chloro substit-
uents. The long Pt-Sn bond found in the crystal
1
structure is also in agreement with the small J SnPt
value found in the 119Sn NMR spectrum.
The sum of the Cl-Sn-Cl angles (295.7°) indicates
that some hybridization has occurred (270° for nonhy-
bridized [SnCl3]-). This deviation is quite small and is
in accordance with the long Pt-Sn distance. The confor-
mation of the trichlorostannyl group is best described
as eclipsed relative to the two equatorial methyl groups,
giving rise to an approximate, noncrystallographic Cs
symmetry of the octahedron. The conformation of the
SnCl3 group may be assisted by weak intramolecular
C-H‚‚‚Cl interactions (3.0738 Å) between the equatorial
Me groups and the SnCl3 chlorine atoms.
F igu r e 1. Displacement ellipsoid plot (50% probability)
of fac-[PtMe3(SnCl3)(bipy)] (2b).
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for fa c-P tMe3(Sn Cl3)(bip y) (2b)
Syn th esis of [P tMe2(R)(bip y)(P P h 3)][Sn Cl3] (3).
Kolla´r et al. reported that addition of triarylphosphine
(P) to Pt(II)-trichlorostannyl complexes [PtCl(SnCl3)-
(P-P)] (P-P ) bidendate diphosphine ligand) resulted in
the formation of stable stannate complexes [PtCl(P)(P-
P)][SnCl3], which were found to be soluble in most
organic solvents.16 In a similar fashion it was possible
to replace the weakly coordinated SnCl3 ligand in
complexes 2 by PPh3, resulting in the formation of
cationic platinum(IV) complexes [PtMe2(R)(bipy)(PPh3)]+
(3) with a noncoordinating [SnCl3]- anion (eq 2).
Bond Lengths
Pt(1)-Sn(1)
Pt(1)-N(1)
Pt(1)-N(2)
Pt(1)-C(1)
Pt(1)-C(2)
2.6497(2)
2.147(3)
2.143(5)
2.065(5)
2.068(8)
Pt(1)-C(3)
Sn(1)-Cl(1)
Sn(1)-Cl(2)
Sn(1)-Cl(3)
2.069(5)
2.3896(9)
2.3981(13)
2.3958(12)
Bond Angles
Sn(1)-Pt(1)-N(1)
Sn(1)-Pt(1)-N(2)
Sn(1)-Pt(1)-C(1)
Sn(1)-Pt(1)-C(2)
Sn(1)-Pt(1)-C(3)
N(1)-Pt(1)-N(2)
N(1)-Pt(1)-C(1)
N(1)-Pt(1)-C(2)
N(1)-Pt(1)-C(3)
N(2)-Pt(1)-C(1)
N(2)-Pt(1)-C(2)
90.87(8)
90.82(8)
90.92(13)
92.31(13)
178.7(2)
77.07(16)
174.3(2)
97.3(2)
N(2)-Pt(1)-C(3)
C(1)-Pt(1)-C(2)
C(1)-Pt(1)-C(3)
C(2)-Pt(1)-C(3)
Pt(1)-Sn(1)-Cl(1)
Pt(1)-Sn(1)-Cl(2)
Pt(1)-Sn(1)-Cl(3)
Cl(1)-Sn(1)-Cl(2)
Cl(1)-Sn(1)-Cl(3)
Cl(2)-Sn(1)-Cl(3)
90.3(2)
88.1(3)
88.25(18)
86.7(2)
119.10(2)
117.97(3)
119.77(3)
98.74(4)
97.91(4)
99.00(4)
90.05(15)
97.4(2)
173.58(7)
The six-coordinated platinum center has a distorted-
octahedral geometry. The equatorial plane is formed by
the bipy and the two methyl ligands, while the apical
positions are occupied by the third methyl group and a
trichlorostannyl group, respectively. The donor atoms
in the equatorial plane are essentially coplanar with the
Pt center (largest deviation 0.069(4) Å). The apical
groups are in a linear arrangement with a Me-Pt-Sn
angle of 178.72(13)°. The largest deviation from the ideal
octahedral geometry arises from the bipy bite angle of
77.09(11)°. The Pt-Sn distance of 2.6497(3) Å is irrefut-
able proof of a direct Pt-Sn bond in the solid state. The
Pt-Me distances have the same length (2.065(4)-2.069-
(4) Å), irrespective of their position to the stannyl ligand.
The three Sn-Cl distances (2.3896(9)-2.3981(13) Å) are
slightly longer than the Sn-Cl bond distances observed
in trichlorostannyl platinum(II) complexes.14
Complexes 3 are highly soluble in CDCl3 and CH2-
Cl2, and elemental analyses were in agreement with the
1
proposed formulation. The H NMR resonances of PtMe
trans to the bipy ligand and the resonances of the
methylene group trans to the phosphorus atom in
complexes 3 display 195Pt satellites and 31P coupling but
no 119Sn satellites. The latter confirms that triphen-
ylphosphine instead of [SnCl3]- is bonded to the plati-
num center. The introduction of PPh3 caused an upfield
shift relative to 2 of ca. 0.23 ppm for the methylene
positioned trans to phosphorus (3a , 3c) and methyl
groups (3b). In addition, a decrease (by ca. 9 Hz) of the
2J HPt values was found for the methylene resonances of
the R substituent. For the signals of the PtMe groups
trans to the bipy ligand, no significant changes in the
Since the SnCl3 ligand is a substituent with moderate
trans influence,1e,f,15 it was expected that the Pt-Me
bond of 2b trans to the stannyl ligand would be longer
(14) (a) Dahlenburg, L.; Mertel, S. J . Organomet. Chem. 2001, 630,
221. (b) Farkas, E.; Kolla´r, L.; Moret, M.; Sironi, A. Organometallics
1996, 15, 1345. (c) Cavinato, G.; De Munno, G.; Lami, M.; Marchionna,
M.; Toniolo, L.; Viterbo, D. J . Organomet. Chem. 1994, 466, 277. (d)
Goel, A. B.; Goel, S.; Vanderveen, D. Inorg. Chim. Acta 1981, 54, L5-
L6.
(15) Musco, A.; Pontellini, R.; Grassi, M.; Sironi, A.; Meille, S. V.;
Ru¨egger, H.; Ammann, C.; Pregosin, P. S. Organometallics 1988, 7,
2130.
(16) (a) Kolla´r, L.; Szalontai, G. J . Organomet. Chem. 1991, 421,
341. (b) Farkas, E.; Kolla´r, L.; Moret, M.; Sironi, A. Organometallics
1996, 15, 1345.

Notes
Organometallics, Vol. 22, No. 5, 2003 1159
0.06 mm3, monoclinic, P21/c (No. 14), a ) 10.5494(1) Å, b )
15.4508(2) Å, c ) 14.6084(1) Å, â ) 130.6525(6)°, V ) 1806.49-
(3) Å3, Z ) 4, F ) 2.285 g/cm3. A total of 39 957 reflections
were measured on a Nonius Kappa CCD diffractometer with
a rotating anode (λ ) 0.710 73 Å) at a temperature of 150(2)
K; 4139 reflections were unique (Rint ) 0.0706). Absorption
correction was performed with PLATON21 (routine DELABS,
µ ) 9.55 mm-1, 0.08-0.54 transmission). The structure was
solved with direct methods (SIR97)22 and refined with
SHELXL9723 against F2 of all reflections. Non-hydrogen atoms
were refined freely with anisotropic displacement parameters.
Methyl hydrogen atoms were refined with a rotating model
and phenyl hydrogen atoms with a riding model; there were
184 refined parameters and no restraints. R values (I > 2σ-
(I)): R1 ) 0.0240, wR2 ) 0.0623. R values: R1 ) 0.0258, wR2
) 0.0634. GOF ) 1.084. The residual electron density was
between -1.37 and 0.77 e/Å3. Molecular illustration, structure
checking, and calculations were performed with the PLATON
package.21
chemical shifts and the 2J HPt values were observed. The
NMR data of complex 3b fit well with the literature data
for the closely related complexes [PtMe3(bipy)(PPh3)]-
[BF4]17 and [PtMe3(bipy)(PPh3)][O3SCF3].18 The 31P
NMR spectra showed a single resonance (δ -0.69 (3a ),
-2.04 (3b), -1.23 (3c), respectively) with 195Pt satellites
(1J PPt ) 972, 984, and 964 Hz, respectively). None of
1
the signals in the H and 31P NMR spectra displayed
tin satellites, in line with the noncoordinating character
of the [SnCl3] anion. The 119Sn NMR spectra of 3a -c
each showed a singlet at δ -48.9, -49.6 and -46.3,
respectively, in close agreement with those found for the
[SnCl3] anion in ionic stannate complexes [AsPh4]-
[SnCl3] (δ -51), [NBun4][SnCl3] (δ -52), and, to a lesser
extent, [PBut H][SnCl3] (δ -30).19
3
Con clu sion
Three novel platinum(IV)-trichlorostannyl complexes
[PtMe2(R)(SnCl3)(bipy)] have been prepared successfully
by the reaction of SnCl2 with [PtClMe2(R)(bipy)] (R )
allyl, Me, Bz). These complexes represent the first
examples of Pt(IV) stannyl complexes that were pre-
pared through SnCl2 insertion into the PtIV-Cl bond.
NMR studies of 2a -c and a crystal structure of 2b prove
the presence of a direct tin-platinum bond. The weakly
coordinated SnCl3 ligand can be easily substituted by
triphenylphosphine, resulting in the ionic [PtMe2(R)-
(PPh3)(bipy)][SnCl3] complexes.
[P tMe2(Bz)(Sn Cl3)(bip y)] (2c). This complex was prepared
by following the same procedure described for 2a from
[PtClMe2(Bz)(bipy)] (135 mg (0.27 mmol), dichloromethane (7.5
mL), and tin(II) chloride (50 mg, 0.27 mmol). The yellow
product was isolated in 80% yield. Crystallization of 2a from
hot CH2Cl2 afforded yellow plate-shaped crystals. Anal. Calcd
for C19H21Cl3N2PtSn: C, 32.72; H, 3.03; N, 4.02; Sn, 17.02.
Found: C, 32.88; H, 3.04; N, 3.93; Sn, 17.18.
[P t Me2(a llyl)(b ip y)(P P h 3)][Sn Cl3] (3a ). fac-[PtClMe2-
(allyl)(bipy)] (95 mg, 0.21 mmol) was dissolved in 10 mL of
CH2Cl2. Next 40 mg (0.21 mmol) of tin(II) chloride and 54 mg
(0.21 mmol) of PPh3 were added to the solution. Stirring for
10 min at room temperature afforded a light yellow solution.
Filtration of the reaction mixture and evaporation of the
solvent gave 169 mg of a yellow solid (90%). Anal. Calcd for
C33H34Cl3N2PPtSn: C, 43.57; H, 3.77; Cl, 11.69; N, 3.08; P,
3.40. Found: C, 43.64; H, 3.85; Cl, 11.54; N, 3.60.
Exp er im en ta l Section
Gen er a l P r oced u r es. All reactions and manipulations
were carried out under an inert atmosphere of N2 using
standard Schlenk techniques. All solvents were dried and
distilled prior to use. [PtMe2(bipy)],20 [PtClMe2(benzyl)-
(bipy)],11a [PtClMe3(bipy)],11b and [PtClMe2(allyl)(bipy)]11c were
prepared according to literature procedures. Anhydrous SnCl2
was used as supplied. Elemental analyses were carried out
by H. Kolbe, Mikroanalytische Laboratorium, Mu¨lheim an der
Ruhr, Germany. NMR spectra were recorded on a Varian
Mercury 200 MHz spectrometer.
fa c-[P tMe3(bip y)(P P h 3)][Sn Cl3] (3b). This complex was
prepared by following the same procedure described for 3a
from fac-[PtClMe3(bipy)] (88 mg, 0.20 mmol), dichloromethane
(5 mL), tin(II) chloride (39 mg, 0.27 mmol), and triphenylphos-
phine (53 mg, 0.20 mmol). The product was obtained as an
off-white solid in quantitative yield. Anal. Calcd for C31H32
Cl3N2PPtSn: C, 42.13; H, 3.65; Cl, 12.04; N, 3.17; P, 3.50.
Found: C, 42.18, H, 3.61; Cl, 12.11; N, 3.15; P, 3.54.
-
[P tMe2(allyl)(Sn Cl3)(bipy)] (2a). To a solution of [PtClMe2-
(allyl)(bipy)] (148 mg, 0.33 mmol) in dichloromethane (7.5 mL)
was added tin(II) chloride (61.6 mg, 0.33 mmol). After a few
minutes an intense yellow solution was formed. The volume
of the solution was reduced in vacuo to 1 mL, and pentane (5
mL) was added to precipitate the product as a yellow solid,
which was isolated by filtration, washed with pentane (5 mL),
and dried in vacuo. The yield was quantitative. Anal. Calcd
for C15H19Cl3N2PtSn: C, 27.83; H, 2.96; Cl, 16.43; N, 4.33.
Found: C, 27.74; H, 3.10; Cl, 16.40; N, 4.26.
fa c-[P tMe3(Sn Cl3)(bip y)] (2b). fac-[PtClMe3(bipy)] (100
mg, 0.23 mmol) was dissolved in dichloromethane (5 mL).
Next, tin(II) chloride (44 mg, 0.23 mmol) was added. The
reaction mixture was stirred for 1 h at room temperature and
filtered. Evaporation of the solvent gave 140 mg (98%) of a
yellow solid. The yellow compound (50 mg) was dissolved in 5
mL of CH2Cl2 and crystallized at -20 °C. After 1 week, light
yellow crystals suitable for an X-ray crystallographic study had
formed. Anal. Calcd for C13H17Cl3N2PtSn: C, 25.13; H, 2.76;
Cl, 17.11; N, 4.51. Found: C, 25.20; H, 2.71; Cl, 17.05; N, 4.43.
Cr ysta l Str u ctu r e Deter m in a tion of 2b. Crystal data:
[P tMe2(Bz)(bip y)(P P h 3)][Sn Cl3] (3c). This complex was
prepared by following the same procedure described for 3a
from fac-[PtClMe2(Bz)(bipy)] (240 mg, 0.47 mmol), dichlo-
romethane (20 mL), tin(II) chloride (89 mg, 0.47 mmol), and
triphenylphosphine (124 mg, 0.47 mmol). The product was
isolated as a yellow solid in 80% yield. Anal. Calcd for C37H36
Cl3N2PPtSn: C, 46.30; H, 3.78; N, 2.92; P, 3.23; Cl, 11.08.
Found: C, 46.18; H, 3.88; N, 2.97; P, 3.30; Cl, 11.19.
-
Ack n ow led gm en t. This work has been supported
by ATOFINA Vlissingen BV and the Dutch Ministry of
Economic Affairs/SENTER and in part (M.L., A.L.S.) by
the Council for Chemical Sciences of The Netherlands
Organization for Scientific Research (CW-NWO).
Su p p or tin g In for m a tion Ava ila ble: Tables of X-ray
crystallographic data for 2b. This material is available free of
charge via the Internet at http://pubs.acs.org.
C
13H17Cl3N2PtSn, fw ) 621.42, yellowish plate, 0.45 × 0.24 ×
OM0207414
(17) Arsenault, G. J .; Anderson, C. M.; Puddephatt, R. J . Organo-
metallics 1988, 7, 2094.
(18) Bayler, A.; Canty, A. J .; Skelton, B. W.; White, A. H. J .
Organomet. Chem. 2000, 595, 296.
(19) Coddington, J . M.; Taylor, M. J . J . Chem. Soc., Dalton Trans.
1989, 2223.
(21) Spek, A. L. PLATON, a Multipurpose Crystallographic Tool;
Utrecht University, Utrecht, The Netherlands, 2000.
(22) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna,
R. J . Appl. Crystallogr. 1999, 32, 115.
(20) Monagham, P. K.; Puddephatt, R. J . J . Organomet. Chem. 1984,
3, 444.
(23) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; University of Go¨ttingen, Go¨ttingen, Germany, 1997.