Synthesis and reactivity of organotin compounds containing the C,P-chelating o-carboranylphosphino ligand [o-C2B10H10PPh2-C,P] (CabC,P). X-ray structures of (CabC,CH2P)SnMe2Br, [(CabC,P)SnMe2]2Pd, and [(CabC,P)SnMe2]Pd(PEt3)Cl

Article abstract of DOI:10.1021/om0007872

The triorganotin halides (Cab^C,P)SnMe₂X (2a, X = Cl; 2b, X = Br) and a tetraorganotin compound (Cab^C,P)SnMe₃ (7), containing the o-carboranylphosphino ligand (Cab^C,P), have been prepared by the reaction of LiCab^C,P (1) with Me₂SnX₂ and Me₃SnCl, respectively. ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR spectroscopy indicate that the tin centers in 2a and 2b are pentacoordinate as a result of intramolecular Sn-P coordination, whereas the tin center in 7 is tetracoordinate. The substitution reactions of 2a using NaI, NaN₃, NaCpFe(CO)₂, and NaB(CN)H₃ afforded the substituted products (Cab^C,P)SnMe₂X (3, X = I; 4, X = N₃; 5, X = CpFe(CO)₂; 6, X = H). The Wurtz-type coupling reaction of 2a with sodium afforded the distannane. The reaction of the distannane 10 with Pd₂(dba)₃·CHCl₃ afforded the bis(stannyl)-palladium complex 11. When compounds 2a and 2b were employed in the reaction with Pd₂(dba)₃, the halo-bridged metal complexes 12a and 12b were isolated. The crystal structures of 9b, 11, and 13 were determined by X-ray structural studies. As a result of the Sn-P interaction, the tin atom in 9b exhibits a distorted trigonal-bipyramidal configuration.

Full text of DOI:10.1021/om0007872

Organometallics 2001, 20, 741-748
741
Syn th esis a n d Rea ctivity of Or ga n otin Com p ou n d s
Con ta in in g th e C,P -Ch ela tin g o-Ca r bor a n ylp h osp h in o
Liga n d [o-C2B10H10P P h 2-C,P ](Ca bC,P ). X-r a y Str u ctu r es of
(Ca bC,CH P )Sn Me2Br , [(Ca bC,P )Sn Me2]2P d , a n d
2
[(Ca bC,P )Sn Me2]P d (P Et3)Cl
Taegweon Lee,† Soon W. Lee,‡ Ho G. J ang,† Sang Ook Kang,*,† and J aejung Ko*,†
Department of Chemistry, Korea University, Chochiwon, Chungnam, 339-700, Korea, and
Department of Chemistry, Sungkyunkwan University, Natural Science Campus,
Suwon, 440-746, Korea
Received September 14, 2000
The triorganotin halides (CabC,P)SnMe2X (2a , X ) Cl; 2b, X ) Br) and a tetraorganotin
compound (CabC,P)SnMe3 (7), containing the o-carboranylphosphino ligand (CabC,P), have
1
been prepared by the reaction of LiCabC,P (1) with Me2SnX2 and Me3SnCl, respectively. H,
13C, 31P, and 119Sn NMR spectroscopy indicate that the tin centers in 2a and 2b are
pentacoordinate as a result of intramolecular Sn-P coordination, whereas the tin center in
7 is tetracoordinate. The substitution reactions of 2a using NaI, NaN3, NaCpFe(CO)2, and
NaB(CN)H3 afforded the substituted products (CabC,P)SnMe2X (3, X ) I; 4, X ) N3; 5, X )
CpFe(CO)2; 6, X ) H). The Wurtz-type coupling reaction of 2a with sodium afforded the
distannane. The reaction of the distannane 10 with Pd2(dba)3‚CHCl3 afforded the bis(stannyl)-
palladium complex 11. When compounds 2a and 2b were employed in the reaction with
Pd2(dba)3, the halo-bridged metal complexes 12a and 12b were isolated. The crystal
structures of 9b, 11, and 13 were determined by X-ray structural studies. As a result of the
Sn-P interaction, the tin atom in 9b exhibits a distorted trigonal-bipyramidal configuration.
In tr od u ction
synthesis of phosphinoalkylchlorostannanes and Pt-
[PPh2(CH2)nSnMe2]2, which provided a mechanistic
model for the double stannylation of unsaturated or-
ganic substrates. We5 have investigated the synthesis
of organotin compounds of the type (CabC,N)SnR1R2X
(A), in which the tin center is pentacoordinate as a
result of intramolecular Sn-N coordination. Such an
Sn-N interaction in these compounds is favored by the
presence of electronegative substituents on tin, such as
a halogen and a carboranyl unit.
Although there is a variety of organotin halides with
C,N-chelating ligands that are bonded to the tin atom
by an Sn-C covalent bond and an Sn-N dative bond,1
organotin compounds containing an intramolecular
coordination of a C,P-chelating ligand have been quite
limited, probably due to the difficulty of their prepara-
tion. Moreover, organotin compounds with phosphines
which are soft bases are known only with strong
acceptors such as monoorganotin trihalides2 and dior-
ganotin dihalides.3 Recently, Weichmann4 reported the
† Korea University.
‡ Sungkyunkwan University.
(1) (a) van Koten, G.; Noltes, J . G. J . Am. Chem. Soc. 1976, 98, 5393.
(b) van Koten, G.; J astrzebski, J . T. B. H.; Noltes, J . G.; Pontenagel,
W. M. G. F.; Kroon, J .; Spek, A. L. J . Am. Chem. Soc. 1978, 100, 5021.
(c) J astrzebski, J . T. B. H.; Boersma, J .; Esch, P. M.; van Koten, G.
Organometallics 1991, 10, 930. (d) J astrzebski, J . T. B. H.; van Koten,
G.; Knaap, C. T.; Schreurs, A. M. M.; Kroon, J .; Spek, A. L. Organo-
metallics 1986, 5, 1551. (e) Rippstein, R.; Kickelbick, G.; Schubert, U.
Inorg. Chim. Acta 1999, 290, 100. (f) Schwarzkopf, K.; Metzger, J . O.;
Saak, W.; Pohl, S. Chem. Ber. 1997, 130, 1539. (g) Pieper, N.; Klaus-
Mrestani, C.; Schu¨rmann, M.; J urkschat, K.; Biesemans, M.; Ver-
bruggen, I.; Martins, J .; Willem, R. Organometallics 1997, 16, 1043.
(h) Dakternieks, D.; Dyson, G.; J urkschat, K.; Tozer, R.; Tiekink, E.
R. T. J . Organomet. Chem. 1993, 458, 29. (i) Zickgraf, A.; Beuter, M.;
Kolb, U.; Dra¨ger, M.; Tozer, R.; Dakternieks, D.; J urkschat, K. Inorg.
Chim. Acta 1998, 275, 203. (j) Hoppe, S.; Weichmann, H.; J urkschat,
K.; Schneider-Koglin, C.; Dra¨ger, M. J . Organomet. Chem. 1995, 505,
63.
We reasoned that intramolecularly coordinated orga-
notin compounds containing a carboranyl unit and a
C,P-substituent (CabC,P) might stabilize the pentacoor-
dinate tin center and be useful starting compounds for
further transformations. We have adopted a systematic
approach to developing this system through the syn-
(2) (a) Silvestri, A.; Rivarola, E.; Barbieri, R. Inorg. Chim. Acta 1977,
23, 149. (b) Iashina, N. S.; Gefel, E. I.; Petrosyan, V. S.; Retov, O. A.
Dokl, Akad, Nauk 1985, 281, 1387.
(4) (a) Weichmann, H. J . Organomet. Chem. 1982, 238, C49. (b)
Weichmann, H. J . Organomet. Chem. 1984, 262, 279.
(5) Lee, J .-D.; Kim, S.-J .; Yoo, D.; Ko, J .; Cho, S.; Kang, S. O.
Organometallics 2000, 19, 1695.
(3) Mullins, F. P.; Curran, C. Can. J . Chem. 1975, 53, 3200.
10.1021/om0007872 CCC: $20.00 © 2001 American Chemical Society
Publication on Web 01/20/2001

742 Organometallics, Vol. 20, No. 4, 2001
Lee et al.
thesis of analogues of (CabC,P)SnMe2X (X ) Cl, Br)
functionalized at tin using the lithium derivative of the
potentially bidentate C,P-chelating o-carboranylphos-
phino ligand system LiCabC,P (1). In this paper, we
describe (i) the facile synthesis of triorganotin halides
containing intramolecular Sn-P coordination; (ii) the
isolation of the distannane by the Wurtz-type coupling
reaction of (CabC,P)SnMe2Cl; (iii) the synthesis of a
stable cyclic bis(o-carboranylstannyl)palladium com-
plex; and (iv) the synthesis of bridged bimetallic com-
plexes by the oxidative addition reaction of (CabC,P)-
SnMe2X with a zerovalent palladium compound.
tion between 2a and sodium azide proceeded cleanly to
1
give compound 4 as colorless crystals. The H, 13C, and
31P NMR spectral data of compounds 3 and 4 are
consistent with the presence of the bidentate o-carbo-
ranylphosphino ligand.
(CabC,P)SnMe2{FeCp(CO)2} (5) was prepared as yel-
low crystals by the reaction of compound 2a with a
stoichiometric amount of NaFeCp(CO)2 (eq 3). Com-
Resu lts a n d Discu ssion
Syn th esis of th e Tr ior ga n otin Ha lid es (Ca bC,P )-
Sn Me2X (2a a n d 2b). Compounds 2a and 2b were
prepared as colorless solids by the reaction of LiCabC,P
(1) with a stoichiometric amount of Me2SnX2 according
to eq 1. Compounds 2a and 2b are soluble in toluene
pound 5 decomposes in air. The signal for Sn-CH3 in
1
the H and 13C NMR spectroscopic data is at a higher
field than that of compounds 2-4. The splitting pattern
due to the coupling of 119Sn and P in the 31P NMR
spectrum is absent. The NMR data suggest that com-
pound 5 is tetracoordinated in solution. This is demon-
strated clearly by the downfield shift of the 119Sn NMR
resonance at 196.5 ppm. It was known that, in the case
of triorganotin halides, the acceptor strength of the tin
atom is so weak that only a few stable adducts with
phosphines were known.6 Accordingly, the presence of
a strong metal nucleophile such as CpFe(CO)2 as a
substituent will not allow adduct formation with the
Lewis base, a phosphorus donor.
1
and THF. The H, 13C, and 31P NMR spectra for 2a and
The triorganotin hydride (CabC,P)SnMe2H (6) com-
pound was prepared by the reaction of compound 2a
with sodium cyanoborohydride as a reducing agent (eq
4). Initially, we attempted the substitution reaction of
2b support the proposed structure. We observed indica-
tions of a weak intramolecular SnrP interaction from
the NMR spectra. The direct evidence for the existence
of an intramolecular SnrP coordination in 2a is pro-
vided by (i) the distinctive splitting pattern in its 1H
NMR spectrum due to coupling of a P atom with the
tin-methyl hydrogen (3J H-P ) 3.00 Hz), (ii) the existence
of a doublet at δ 3.40 (2J C-P ) 13.06 Hz) in its 13C NMR
spectrum due to coupling of the tin-methyl carbon and
a phosphorus atom, and (iii) the observation of a singlet
with 117,119Sn satellites, at δ 29.71 (1J
) 74.3 Hz)
) 72.6
31P-119Sn
31
in its P NMR spectrum, at δ 108.3 (1J
119Sn-31
P
Hz) in its 119Sn NMR spectrum by coupling of the 119Sn
and P atoms. The downfield shifts and the low values
compound 2a with LiAlH4 at room temperature, but
decomposition occurred. After many attempts, we found
that sodium cyanoborohydride, a mild reducing agent,
served well in the conversion of the tin chloride to the
tin hydride without any cleavage of the Sn-C (carbo-
1
of the coupling constants of the H, 13C, and 31P NMR
spectra for 2a and 2b compared with those for the
phosphinoalkylchlorostannanes of the type Me2SnCl-
(CH2)nPR1R2 (n ) 2, 3) indicate that the compounds 2a
and 2b have weaker SnrP interaction.4
Compound 2a was found to be a good starting mate-
rial for further transformations. When a colorless
toluene-d8 solution of 2a was treated at ambient tem-
perature with sodium iodide, a yellow color developed
within 2 h. Analysis of this solution by 1H NMR
spectroscopy showed clean conversion to the product 3,
which was isolated and characterized (eq 2). The reac-
1
rane) bond. An H NMR signal ascribable to the Sn-H
3
bond was observed at 6.23 (2J H-P ) 10.2 Hz, J H-H
)
1.8 Hz) ppm. The 31P NMR spectrum of 6 shows the
expected pattern of a singlet (1J
) 71.6 Hz) at
25.12 ppm. The infrared spectrum of 6 shows the
31P-119Sn
stretching mode of ν(SnH) at 1878 cm-1
.
Syn t h esis of t h e Tet r a or ga n ot in Com p lex
(CabC,P )Sn Me3 (7). (CabC,P)SnMe3 was prepared readily
in high yield by the reaction between LiCabC,P and Me3-
1
SnCl. The signal for Sn(CH3) in the H NMR spectrum
is at a higher field compared with that of the triorga-
notin halides (CabC,P)SnMe2X. However, the splitting
pattern and coupling constants are comparable to those
of (CabC,P)SnMe2X (2a and 2b). The 119Sn NMR spec-
trum of 7 shows a resonance at 106.4 ppm. The chemical
(6) Weichmann, H.; Meunier-Piret, J .; Van Meerssche, M. J . Orga-
nomet. Chem. 1986, 309, 267.

Synthesis and Reactivity of Organotin Compounds
Organometallics, Vol. 20, No. 4, 2001 743
F igu r e 1. X-ray crystal structure of 9b with 50% probability thermal ellipsoids depicted. Selected bond lengths (Å) and
angles (deg): Sn(1)-P(1) 3.188(1), Sn(1)-Br(1) 2.5568(7), Sn(1)-C(1) 2.204(4), C(1)-Sn(1)-Br(1) 96.49(9).
shift is consistent with prior observations of a five-
coordinated Sn atom. The compound is unusual in that
our previous study demonstrated that the tetraorgano-
tin complex (CabC,N)SnMe3 has a tetrahedral ligand
arrangement around the tin atom. Accordingly, this
could involve a weak intramolecular interaction between
the tin and phosphorus atoms.
the coordination environment about Sn(1) may be
described as slightly distorted trigonal bipyramidal.
Such distorted geometry was found in other structural
reports on {3-[tert-butyl(phenyl)phosphino]propyl}dimeth-
yltin chloride.6 The Sn(1)-P(1) intramolecular interac-
tion distance (3.188(1) Å) is comparable to that observed
for Me2SnCl[(CH2)3PR2] (3.078 Å). On the basis of an
average value of 2.52 Å for the few known Sn-P single
bond lengths,7 the Sn-P distance of 3.188(1) Å in 9b
indicates that the Sn-P intramolecular coordination is
weak. The Sn-Br bond distance (2.5568(7) Å) shows a
slight lengthening, which falls in the range observed for
other pentacoordinated adducts of triorganotin halides.8
Syn th esis of th e F ive-Mem ber ed Tr ior ga n otin
Ha lid es (Ca b C,CH P )Sn Me2X (9a a n d 9b). Although
2
the triorganotin halides (CabC,P)SnMe2X with an in-
tramolecular SnrP coordination are well established,
we believed that the compounds have a relatively weak
Sn-P interacton due to the rigidity of the carborane
backbone. A more suitable alternative ligand for a
stronger SnrP interaction is the five-membered biden-
tate phosphinomethylcarboranyl ligand. This proved to
The H, 13C, 31P, and 119Sn NMR spectra of 9b were
1
consistent with the structure determined by X-ray
crystallography. 1H NMR signals ascribable to the
be the case. The reaction between LiCabC,CH P (8) and
2
3
SnMe2 and CH2 were observed at 1.19 (d, J H-P ) 4.2
Me2SnX2 (X ) Cl, Br) proceeds cleanly to give (CabC,CH P)-
2
2
2
119Sn
Hz, J H-
117Sn
) 67.5 Hz, J H-
) 63.6 Hz) and 3.25
SnMe2X as colorless crystals (eq 5).
2
(d, J H-P ) 2.1 Hz) ppm, respectively. The 31P NMR
1
31P-119Sn
signal had shifted from 29.12 (s, J
) 48.6 Hz)
ppm for (CabC,P)SnMe2Br to 35.22 ppm with a big
coupling constant of J P-Sn (55.2 Hz). The 119Sn NMR
1
chemical shift of -30.2 ppm as a doublet strongly
resembles the literature value for the intramolecular
P-functional triorganotin halides.4b
Syn th esis of th e Bis(o-ca r bor a n ylp h osp h in o)-
d ista n n a n e, [(Ca bC,P )Sn Me2]2 (10). The Wurtz-type
coupling reaction of 2a using sodium afforded the
corresponding distannane containing pseudo-tetracoor-
dinate tin centers (eq 6). The reaction of 2a with 5 equiv
Compounds 9a and 9b are moderately soluble in
toluene and THF. The structure of 9b, unambiguously
established by single-crystal X-ray analysis, is shown
in Figure 1. Crystallographic data and processing
parameters are given in Table 1. Atoms C(1), C(3), and
C(4) constitute a basal plane, while the coordination
sphere of Sn(1) is completed by P(1) and Br(1) residing
in the axial positions. Because the P(1)-Sn(1)-Br(1)
bond angle is 168.4(3)° and the sum of the bond angles
surrounding the Sn atom on the basal plane is 358.2°,
(7) (a) Mathiasch, B. J . Organomet. Chem. 1979, 165, 295. (b)
Dra¨ger, M.; Mathiasch, B. Angew. Chem. 1981, 93, 1079.
(8) (a) Swami, K.; Hutchinson, J . P.; Kuivila, H. G.; Zubieta, J . A.
Organometallics 1984, 3, 1687. (b) Buckle, J .; Harrison, P. G.; King,
T. J .; Richards, J . A. J . Chem. Soc., Dalton Trans. 1975, 1552.
(9) Piers, E.; Skerlj, R. T. J . Org. Chem. 1987, 52, 4421.
(10) Tsuji, Y.; Kakehi, T. J . Chem. Soc., Chem. Commun. 1992, 1000.
(11) Mitchell, T. N.; Schneider, U. J . Organomet. Chem. 1991, 407,
319.

744 Organometallics, Vol. 20, No. 4, 2001
Ta ble 1. Cr ysta l Da ta of 9b, 11, a n d 13
Lee et al.
9b
11
13
empirical formula
molecular weight
cryst syst
space group
a (Å)
C
17H28B10BrPSn
C32H52B20P2PdSn2
1058.66
monoclinic
P21/c
12.106(1)
16.056(2)
23.321(2)
95.077(7)
4515.2(8)
4
C22H31B10Cl P2PdSn
726.05
orthorhombic
Pnma
12.840(1)
15.035(2)
570.06
monoclinic
C2/c
27.071(4)
14.322(2)
14.151(3)
113.272(9)
5040(1)
8
b (Å)
c (Å)
17.247(1)
â (deg)
V, Å3
3329.4(5)
4
1.448
Z value
D(calcd) (g cm-3
cryst size, mm
F(000)
)
1.503
1.557
0.80 × 0.60 × 0.28
0.62 × 0.60 × 0.24
0.28 × 0.20 × 0.20
2240
1792
1424
µ (mm-1
)
2.677
1.589
1.479
2θ range (deg)
scan type
4.06-50
3.5-50
3.5-50
ω
ω
ω
no. of reflns measd
4461
8097
3318
no. of obsd reflns (I > 2σ(I))
4364
7698
0.0343
0.0836
1.099
3026
R
0.0358
0.0912
1.038
0.0462
0.1167
1.061
a
wR2
goodness of fit
wR2 ) ∑[w(Fo - Fc2)2]/∑[w(Fo2)2]1/2
.
a
2
of sodium in toluene at room temperature for 3 h gave
Sn to the palladium to afford the bis(stannyl)palladium
complex 11 as colorless crystals in 34% yield (eq 7).
Complex 11 is stable in an inert-gas environment and
shows slow decomposition when in contact with air. It
is readily soluble in organic solvents such as aromatic
hydrocarbons and THF.
the distannane [(CabC,P)SnMe2]2 (10) in 46% yield.
The composition of 10 was established by elemental
1
analysis. The H, 13C, and 31P NMR spectra of 10 also
are consistent with its assigned structure. The signals
1
for Sn(CH3) in the H NMR spectrum are at a higher
field than for the intramolecular tin compounds (2-4).
In particular, the 31P NMR signal had clearly shifted
1
31P-119Sn
from 29.71 (d, J
) 74.3 Hz) ppm for (CabC,P)-
SnMe2Cl to -12.78 ppm as a singlet. The NMR data
suggest that compound 10 is tetracoordinated in solu-
tion and has no interaction between tin and phosphorus.
This is demonstrated most clearly by the downfield shift
of the 119Sn NMR resonance at 162.6 ppm.
Syn th esis of th e Bis(sta n n yl)p a lla d iu m Com p lex
(Ca bC,P )2P d (11). Bis(stannyl)palladium complexes
have been implicated as key intermediates in the double
stannylation of alkynes,9 1,3-dienes,10 and allenes.11
However, only a few bis(stannyl)complexes have been
fully characterized.11 The complexes were found to be
formed by the oxidative addition reaction of organodis-
tannane with palladium compounds. Compound 10 was
chosen as a good candidate for the oxidative addition
reaction because the tin atom is anchored to the
palladium atom through the chelating phosphine teth-
ers.
The molecular structure of 11 has been determined
by X-ray diffraction. The structure is given in Figure 2,
and crystallographic data are given in Table 1. Complex
11 has a square-planar geometry with cis-arrangement
of the two tin atoms. The Pd-Sn bond distance (2.5743-
(5)-2.5760(5) Å) of 11 is in agreement with the corre-
sponding values observed in (dtbpe)PdH(SnMe3) (2.573-
(2) Å)12 and Pd[η2-(SiMe2CH2CH2PPh2)][η2-(SnMe2-
CH2CH2PPh2)] (2.573(2) Å).13 The distance between Sn-
(1) and Sn(2) (3.2612(5) Å) suggests the presence of
Treatment of the distannane 10 with Pd2(dba)3‚CHCl3
(dba ) dibenzylideneacetone) in toluene at room tem-
perature resulted in the oxidative addition of the Sn-
1
considerable Sn-Sn interaction. The H, 13C, and 31P
NMR spectra of 11 were consistent with the structure
determined by X-ray crystallography. In particular, the
31P NMR spectrum of 11 showed a resonance centered
(12) Trebbe, R.; Schager, F.; Goddard, R.; Po¨rschke, K.-R. Organo-
metallics 2000, 19, 521
(13) Murakami, M.; Yoshida, T.; Kawanami, S.; Ito, Y. J . Am. Chem.
Soc. 1995, 117, 6408.
(14) Obora, Y.; Tsuji, Y.; Nishiyama, K.; Ebihara, M.; Kawamura,
T. J . Am. Chem. Soc. 1996, 118, 10922.
2
at 78.50 ppm with satellite peaks due to J P-Sn(transoid)
(2054.8 Hz with 119Sn and 1943.0 Hz with 117Sn),
2
2J P-
(207.7 Hz), and J P-
119Sn(cisoid)
117Sn(cisoid)
(194.2 Hz).

Synthesis and Reactivity of Organotin Compounds
Organometallics, Vol. 20, No. 4, 2001 745
F igu r e 2. X-ray crystal structure of 11 with 50% probability thermal ellipsoids depicted. Selected bond lengths (Å) and
angles (deg): Sn(1)-C(1) 2.213(4), Sn(1)-Pd(1) 2.5760(5), Sn(1)-Sn(2) 3.2612(5), Sn(2)-C(3) 2.215(5), Sn(2)-Pd(1) 2.5743-
(5), Pd(1)-P(1) 2.345(1), Pd(1)-P(2) 2.349(1), P(1)-C(2) 1.896(4), P(2)-C(4) 1.908(4), C(1)-Sn(1)-Pd(1) 100.73(11), C(3)-
Sn(2)-Pd(1) 99.27(12), P(1)-Pd(1)-P(2) 104.23(4), P(1)-Pd(1)-Sn(2) 166.87(3), P(2)-Pd(1)-Sn(2) 88.89(3), P(1)-Pd(1)-
Sn(2) 88.44(3), P(2)-Pd(1)-Sn(1) 165.87(3), Sn(2)-Pd(1)-Sn(1) 78.573(14).
These values resemble the literature values for the cis-
cyclic bis[(diphenylphosphinoethyl)diorganosilyl]platinum
complexes have been prepared by the reaction of Ph2-
PCH2CH2SiHR1R2 with Pt(cod)2.16
14
{Pt[PPh2(CH2)2SnMe2]2}4a and Pt(SnMe3)2(PR3)2 com-
plexes.
We have also carried out the reaction of 1-PPh2-2-
SnMe2H-1,2-C2B10H10 (6) with Pd2(dba)3 in toluene in
an alternative synthesis of complex 11, which was
isolated as colorless crystals in 80% yield (eq 8). It was
Syn th esis of th e Br id ged Dip a lla d iu m Com p lex
[(Ca bC,P )2P d (µ-X)]2 (12a a n d 12b). To determine how
the five-coordinate tin complexes 2a and 2b would react
with the low-valent metal complexes, the reaction of 2a
and 2b with Pd2(dba)3 was investigated. Consequently,
when compounds 2a and 2b were employed as starting
compounds in the reaction with Pd2(dba)3, the halo-
bridged dipalladium metal complexes 12a and 12b were
isolated as yellow crystals in high yield (eq 9). The
well established that hydrosilylation of low-valent metal
complexes by the functional silane PPh2CH2CH2SiMe2H15
has provided access to a family of new bis-chelate
derivatives of the silyl PPh2CH2CH2SiMe2- in which a
silicon-transition metal bond is supported by simulta-
neous phosphine coordination to the metal atom. Such
(15) Grundy, S. L.; Holmes-Smith, R. D.; Stobart, S. R.; Williams,
M. A. Inorg. Chem. 1991, 30, 3333.
(16) Holmes-Smith, R. D.; Stobart, S. R.; Cameron, T. S.; J ochem,
K. J . Chem. Soc., Chem. Commun. 1981, 937.
yellow products 12a and 12b are moderately stable in
air and decompose slowly on contact with moisture.
Compounds 12a and 12b are soluble in toluene and

746 Organometallics, Vol. 20, No. 4, 2001
Lee et al.
F igu r e 3. X-ray crystal structure of 13 with 50% probability thermal ellipsoids depicted. Selected bond lengths (Å) and
angles (deg): Sn(1)-C(1) 2.222(8), Sn(1)-Pd(1) 2.5169(8), Pd(1)-P(2) 2.281(2), Pd(1)-P(1) 2.338(2), Pd(1)-Cl(1) 2.417(2),
P(1)-C(2) 1.883(8), C(1)-Sn(1)-Pd(1) 101.2(2), P(2)-Pd(1)-P(1) 176.86(8), P(2)-Pd(1)-Cl(1) 88.48(8), P(1)-Pd(1)-Cl(1)
94.66(8), P(2)-Pd(1)-Sn(1) 86.14(6), P(1)-Pd(1)-Sn(1) 90.73(5), Cl(1)-Pd(1)-Sn(1) 174.61(6).
1
THF and were characterized by H, 13C, and 31P NMR
two signals are observed at 80.49 and -94.53 ppm for
the inequivalent 31P nuclei, for which the coupling 2J P-P
1
and elemental analysis. The H NMR signal for SnMe2
is large. The large couplings (2J
) 428.8 Hz)
31P-31
P
in 12a is at higher field (0.42 ppm) than that for
compound 2a . In particular, the 31P NMR signals had
indicate that the two phosphorus atoms are trans.
clearly shifted from 29.71 (1J
) 74.3 Hz) ppm
31P-119Sn
The structure of 13 was unambiguously established
by single-crystal X-ray analysis. The molecular struc-
ture of 13 is shown in Figure 3. The plane of symmetry
of the molecule coincides with the crystallographic plane
of symmetry. This is why the compound has a Z value
of 4 instead of 8. The plane of symmetry passes through
Sn(1), Pd(1), Cl(1), P(1), P(2), B(5), C(1), C(2), C(12), and
C(13) atoms. This symmetry clearly explains that seven
atoms (Pd(1), Sn(1), P(1), P(2), Cl(1), C(1), and C(2)) are
perfectly coplanar and also that the equatorial plane
(Pd(1), Sn(1), P(1), P(2), and Cl(1)) of the Pd moiety is
perfectly planar. The Pd-Sn distance (2.5169(8) Å) of
13 conforms to literature expectations (2.554-2.595
Å).17
for (CabC,P)SnMe2Cl to 91.37 ppm with a rather big
coupling constant of J P-Sn (208.6 Hz). The 119Sn spec-
2
trum of 12a showed a resonance at -118.3 ppm.
Compound 12a is easily cleaved by an external strong
donor ligand such as triethylphosphine to give the
mononuclear palladium compound 13 (eq 10). The
In summary, we have isolated intramolecularly co-
ordinated organotin compounds of the type (CabC,P)-
SnMe2X containing the C,P-substituent. The compound
(CabC,P)SnMe2Cl readily undergoes a substitution reac-
tion with NaI, NaN3, and NaFeCp(CO)2 to afford the
substituted products. The compound 2a also undergoes
a Wurtz-type coupling reaction with Na to give the
distannane compound. A bis(stannyl)palladium complex
was prepared by the oxidative addition reaction of the
distannane or by dehydrostannylation of the chelated
formulation of 13 was established by elemental analysis.
Furthermore, the spectroscopic data (1H, 13C, and 31P
NMR) for 13 also are consistent with its assigned
(17) (a) Braunstein, P.; Knorr, M.; Piana, H.; Schubert, U. Organo-
metallics 1991, 10, 828. (b) Musco, A.; Pontellini, R.; Grassi, M.; Sironi,
A.; Meille, S. V.; Ru¨egger, H.; Ammann, C.; Pregosin, P. S. Organo-
metallics 1988, 7, 2130.
1
structure. The H NMR spectrum consists of a singlet
due to the SnMe at 0.59 ppm. In the 31P NMR spectrum,

Synthesis and Reactivity of Organotin Compounds
Organometallics, Vol. 20, No. 4, 2001 747
7.71-7.43 (m, 10H, PPh2), 1.25 (d, 6H, 3J H-P ) 3.0 Hz, 2J H-
119
tin hydride by Pd2(dba)3. Compound 2a undergoes an
oxidative addition reaction with Pd2(dba)3 to afford the
bridged dipalladium complex, which is easily cleaved
by a donor ligand to give the mononuclear metal
compound. Compound 2a was found to be a good
starting material. This potential has been further
exploited in a series of novel chemical transformations
with this system.
Sn
2
117
) 65.7 Hz, J H-
) 44.7 Hz, Sn-CH3). 13C{1H} NMR
Sn
(CDCl3): δ 134.64, 134.38, 132.22, 131.67, 129.32, 128.96 (Ph),
2
4.21 (d, J C-P ) 17.62 Hz, Sn-C). 31P NMR (CDCl3): δ 28.32
1
31
119
P- Sn
(s, J
) 56.2 Hz, PPh2). Anal. Calcd for C16H26B10IPSn:
C, 31.88; H, 4.31. Found: C, 31.42; H, 4.18.
1-Dip h en ylp h osp h in o-2-a zid od im et h ylt in -1,2-ca r b o-
r a n e (4). To a stirred toluene solution (15 mL) of 2a (0.07 g,
0.137 mmol) was added NaN3 (0.044 g, 0.685 mmol) at room
temperature, and the mixture was refluxed for 48 h. After
filtering through Celite, the solution was concentrated under
reduced pressure to incipient crystallization and stored in a
ca. -10 °C freezer to give 4 as colorless crystals. Yield: 67%,
mp 198 °C. 1H NMR (CDCl3): δ 7.68-7.26 (m, 10H, PPh2),
Exp er im en ta l Section
All experiments were performed under a dry nitrogen
atmosphere in a Vacuum Atmospheres drybox or by standard
Schlenk techniques. Toluene and THF were freshly distilled
from sodium benzophenone. Hexane was dried and distilled
from CaH2. 1H, 13C, 31P, and 119Sn NMR spectra were recorded
on a Varian Mercury 300 spectrometer operating at 300.00,
75.44, 121.44, and 111.82 MHz, respectively. Chemical shifts
were referenced to TMS (1H), benzene-d6 (1H, δ 7.156; 13C{1H},
δ 128.00), and H3PO4. IR spectra were recorded on a Biorad
FTS-165 spectrometer. Elemental analyses were performed
with a Carlo Erba Instruments CHNS-O EA 1108 analyzer.
o-Carborane was purchased from the Callery Chemical Co.
and used without purification. The starting materials, Pd2-
(dba)3, {CpFe(CO)2}2, and Me2SnX2 (X ) Cl, Br), were pur-
chased from Strem Chemical. 1-PPh2-1,2-C2B10H1018 and 1-PPh2-
CH2-1,2-C2B10H1019 were prepared according to the literature.
1-Dip h en ylp h osp h in o-2-ch lor od im eth yltin -1,2-ca r bo-
r a n e (2a ). To a stirred toluene solution (15 mL) of 1-PPh2-
1,2-C2B10H10 (0.3 g, 0.91 mmol) was added a solution of
n-butyllithium in hexane (0.7 mL, 1.6 M, 1.12 mmol) at 0 °C.
The reaction mixture was allowed to warm to ambient tem-
perature and was stirred for 12 h. The reaction mixture was
cooled to -78 °C, and a solution of Me2SnCl2 (0.2 g, 0.91 mmol)
was added to the reaction mixture at that temperature. The
reaction mixture was warmed to ambient temperature and
stirred for 8 h, followed by filtration on a Celite pad. All
volatiles were removed under reduced pressure and washed
with hexane (15 mL × 3). Recrystallization from toluene gave
the title compound (0.35 g, 74%) as colorless crystals, mp 188-
190 °C. 1H NMR (CDCl3): δ 7.70-7.42 (m, 10H, PPh2), 1.06
3
2
2
119
117
0.93 (d, 6H, J H-P ) 2.1 Hz, J H-
) 66.2 Hz, J H-
)
Sn
Sn
62.8 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 135.06, 134.72,
134.13, 131.06, 129.68, 128.43 (Ph), 8.06 (d, 2J C-P ) 14.72 Hz,
1
Sn-C). 31P NMR (CDCl3): δ 31.06 (s,
J
31
119
) 58.1 Hz,
P- Sn
PPh2). IR (KBr pellet, cm-1): ν 2084 (N3). Anal. Calcd for
C
16H26B10N3PSn: C, 37.11; H, 5.02. Found: C, 36.84; H, 4.93.
1-P P h 2-2-Sn Me2{FeCp(CO)2}-1,2-C2B10H10 (5). To a stirred
toluene solution (15 mL) of 2a (0.07 g, 0.137 mmol) was added
NaCpFe(CO)2 (0.03 g, 0.150 mmol) at room temperature, and
the mixture was stirred for 8 h. After filtering through Celite,
the solution was concentrated under reduced pressure to
incipient crystallization and stored in a ca. -15 °C freezer to
give 5 as yellow crystals. Yield: 77%, mp 168-171 °C. 1H NMR
(CDCl3): δ 7.67-7.26 (m, 10H, PPh2), 4.87 (s, 5H, C5H5,), 0.55
2
(s, 6H, J H-Sn ) 42.9 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ
213.53 (CO), 134.61, 134.41, 131.54, 130.22, 128.66, 128.60
(Ph), 82.11 (C5H5), -9.23 (Sn-C). 31P NMR (CDCl3): δ 24.37
(PPh2). 119Sn NMR (CDCl3): δ 196.5. IR (KBr pellet, cm-1) ν
2001, 1944 (CtO). Anal. Calcd for C23H31O2B10PFeSn: C,
42.31; H, 4.75. Found: C, 41.96; H, 4.58.
1-Dip h en ylp h osp h in o-2-h yd r id od im et h ylt in -1,2-ca r -
bor a n e (6). To a stirred toluene solution (15 mL) of 2a (0.25
g, 0.49 mmol) was added NaBH3CN (0.063 g, 1.00 mmol, 1 M
in THF) at room temperature, and the mixture was stirred
for 1 day at that temperature. After filtering through Celite,
all volatiles were removed in vacuo. Then 6 was yielded as
sticky white powder. Yield: 92%, mp 123-126 °C. 1H NMR
(CDCl3): δ 7.81-7.26 (m, 10H, PPh2), 6.23 (dsep, 1H, 1J H-
119
Sn
3
2
2
119
117
(d, 6H, J H-P ) 3.00 Hz, J H-
) 68.4 Hz, J H-
) 62.4
2
3
Sn
Sn
) 2055.6 Hz, J H-P ) 10.2 Hz, J H-H ) 1.8 Hz, Sn-H). 0.54
Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 134.72, 134.43, 131.56,
3
3
2
119
(dd, 6H, J H-H ) 1.8 Hz, J H-P ) 1.2 Hz, J H-
) 61.2 Hz,
Sn
129.13, 129.06, 129.00 (Ph), 3.40 (d, 2J C-P ) 13.06 Hz, Sn-C).
2
J H-
) 56.7 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 136.42,
117
Sn
31
1
31
119
P NMR (CDCl3): δ 29.71 (s, J
NMR (CDCl3): δ 108.3 (d, J
) 74.3 Hz, PPh2). 119Sn
) 72.6 Hz). Anal. Calcd
2
P- Sn
135.25, 132.75, 130.22, 127.97 (Ph), -6.44 (d, J C-P ) 15.76
1
119
31
31
1
Sn-
P
31
119
Hz, Sn-C). P NMR (CDCl3): δ 25.12 (s, J
) 71.6 Hz,
P- Sn
for C16H26B10ClPSn: C, 37.55; H, 5.08. Found: C, 37.24; H,
4.98.
PPh2). 119Sn NMR (CDCl3): δ -52.8 (d, J H-
) 2055.6 Hz,
1
119
Sn
1
J
) 68.4 Hz). IR (KBr pellet, cm-1): ν 1878 (Sn-H).
119
31
Sn-
P
1-Dip h en ylp h osp h in o-2-br om od im eth yltin -1,2-ca r bo-
r a n e (2b). The same procedure was used as described for 2a
except dibromodimethyltin was used instead of dichlorodi-
Anal. Calcd for C16H27B10PSn: C, 40.29; H, 5.66. Found: C,
40.03; H, 5.47.
1-Diph en ylph osph in o-2-tr im eth yltin -1,2-car bor an e (7).
The same procedure was used as described for 2a except
trimethyltin chloride (0.2 g, 1.00 mmol) was used instead of
dichlorodimethyltin. In this case, cold hexane (5 mL) was used
for washing. Yield: 62%, mp 228 °C. 1H NMR (CDCl3): δ 7.71-
1
methyltin. Yield: 67%, mp 188-190 °C. H NMR (CDCl3): δ
7.72-7.39 (m, 10H, PPh2), 1.14 (d, 6H, 3J H-P ) 4.5 Hz, 2J H-
119
Sn
2
) 101.1 Hz, J H-
) 92.4 Hz, Sn-CH3). 13C{1H} NMR
117
Sn
(CDCl3): δ 134.85, 134.40, 132.04, 131.52, 129.18, 128.99 (Ph),
2
4.08 (d, J C-P ) 21.04 Hz, Sn-C). 31P NMR (CDCl3): δ 29.12
3
2
119
7.41 (m, 10H, PPh2), 0.43 (d, 9H, J H-P ) 15.0 Hz, J H-
)
Sn
1
) 48.6 Hz, PPh2). 119Sn NMR (CDCl3): δ 96.4 (d,
31
119
(s, J
J
57.2 Hz, J H-
)
54.3 Hz, Sn-CH3). 13C{1H} NMR
P- Sn
31
2
117
Sn
1
119
) 118.8 Hz). Anal. Calcd for C16H26B10BrPSn: C,
Sn-
P
(CDCl3): δ 136.22, 133.55, 132.06, 129.97, 129.51, 127.91 (Ph),
34.57; H, 4.68. Found: C, 34.74; H, 4.76.
2
-4.27 (d, J C-P ) 9.13 Hz, Sn-C). 31P NMR (CDCl3): δ 23.38
1-Dip h e n ylp h osp h in o-2-iod od im e t h ylt in -1,2-ca r b o-
r a n e (3). To a stirred toluene soution (10 mL) of 2a (0.1 g, 0.2
mmol) was added NaI (0.03 g, 0.2 mmol) at room temperature,
and the mixture was stirred for 8 h at that temperature. The
reaction mixture was filtered. The colorless solution was
reduced to incipient crystallization and stored in a ca. -10 °C
1
(s,
(d,
J
J
) 62.2 Hz, PPh2). 119Sn NMR (CDCl3): δ 106.4
) 108.3 Hz). Anal. Calcd for C17H29B10PSn: C,
31
119
P- Sn
1
119 31
Sn-
P
41.59; H, 5.91. Found: C, 41.24; H, 5.72.
1-P P h 2CH2-2-ClSn Me2-1,2-C2B10H10 (9a ). To a stirred
hexane solution (20 mL) of 1-PPh2CH2-1,2-C2B10H10 (0.25 g,
0.73 mmol) was added a solution of n-butyllithium in hexane
(0.55 mL, 1.6 M, 0.88 mmol) at 0 °C. The reaction mixture
was allowed to warm to ambient temperature and was stirred
for 8 h. The solvent was removed in vacuo and dissolved in
toluene (15 mL). The reaction mixture was cooled to -78 °C,
and a toluene solution (10 mL) of Me2SnCl2 (0.19 g, 0.876
1
freezer to give 3. Yield: 78%, mp 172 °C. H NMR (CDCl3): δ
(18) Vin˜as, C.; Benakki, R.; Teixidor, F.; Casabo´, J . Inorg. Chem.
1995, 34, 3844.
(19) Park, J .; Kim, S.; Ko, J .; Park, K.; Cho, S.; Lee, C.-H.; Lee, Y.-
H.; Kang, S. O. Bull. Kor. Chem. Soc. 1998, 19, 363.

748 Organometallics, Vol. 20, No. 4, 2001
Lee et al.
mmol) at -78 °C was added to the reaction mixture and stirred
for 5 h. After filtering through Celite, the solution was
concentrated under reduced pressure to incipient crystalliza-
tion and stored in a ca. -15 °C freezer to give 9a as colorless
crystals. Yield: 75%, mp 201-203 °C. 1H NMR (CDCl3, 25
the solution was reduced to 5 mL, and it was cooled to -15 °C
for 48 h. Complex 12a was obtained as yellow crystals in 88%
yield, mp 196 °C. 1H NMR (CDCl3, 25 °C): δ 8.18-7.56 (m,
20H, PPh2), 0.42 (s, 12H, 2J H-Sn ) 56.4 Hz, Sn-CH3). 13C{1H}
NMR (CDCl3): δ 136.02, 135.82, 132.69, 129.44, 128.65,
128.50, (Ph), -1.53 (s, Sn-C). 31P NMR (CDCl3): δ 91.37 (s,
2
°C): δ 7.71-7.35 (m, 10H, PPh2), 3.27 (d, 2H, J H-P ) 2.7 Hz,
CH2), 1.10 (d, 6H, 3J H-P ) 4.2 Hz, 2J H-
) 73.8 Hz, 2J H-
J
) 208.6 Hz, PPh2). 119Sn NMR (CDCl3): δ -118.3
2
119
117
31
119
Sn
Sn
P- Sn
) 65.1 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 132.87, 132.35,
131.26, 130.11, 129.84, 128.81(Ph), 35.09 (d, 2J C-P ) 12.27 Hz,
(d, J
) 189.8 Hz). Anal. Calcd for C32H52B20Cl2P2 Pd2-
2
119
31
Sn-
P
Sn2: C, 31.10; H, 4.21. Found: C, 30.84; H, 4.08.
2
CH2), 5.22 (d, J C-P ) 26.55 Hz, Sn-C). 31P NMR (CDCl3): δ
P r ep a r a t ion of [(1-P P h 2-2-Sn Me2-1,2-C2B10H 10)P d (µ-
Br )]2 (12b). The same procedure was used as described for
12a except 2b was used instead of 2a . Yield: 85%, mp 200
°C. 1H NMR (CDCl3, 25 °C): δ 8.16-7.56 (m, 20H, PPh2), 0.44
(s, 12H, 2J H-Sn ) 56.1 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ
136.00, 135.80, 132.70, 129.54, 128.60, 128.44, (Ph), -0.39 (s,
1
31
119
34.18 (s, J
) 54.0 Hz, PPh2). Anal. Calcd for C17H28B10-
ClPSn: C, 38.85; H, 5.33. Found: C, 38.96; H, 5.44.
P- Sn
1-P P h 2CH2-2-Br Sn Me2-1,2-C2B10H10 (9b). The same pro-
cedure was used as described for 9a except dibromodimethyltin
was used instead of dichlorodimethyltin. Yield: 79%, mp 204-
207 °C. 1H NMR (CDCl3, 25 °C): δ 7.42-7.16 (m, 10H, PPh2),
3.25 (d, 2H, 2J H-P ) 2.1 Hz, CH2), 1.19 (d, 6H, 3J H-P ) 4.2 Hz,
2
Sn-C). 31P NMR (CDCl3): δ 93.67 (s,
J
) 215.5 Hz,
) 217.4 Hz).
31
119
P- Sn
2
PPh2). 119Sn NMR (CDCl3): δ -132.5 (d, J
119 31
Sn-
P
2
2
) 67.5 Hz, J H-
) 63.6 Hz, Sn-CH3). 13C{1H}
119
J H-
117
Sn
Sn
Anal. Calcd for C32H52B20Br2P2Pd2Sn2: C, 29.02; H, 3.93.
Found: C, 28.85; H, 3.82.
NMR (CDCl3): δ 133.04, 132.24, 132.02, 131.44, 130.26, 128.64
2
2
(Ph), 36.22 (d, J C-P ) 12.84 Hz, CH2), 5.42 (d, J C-P ) 26.82
P r ep a r a tion of (1-P P h 2-2-Sn Me2-1,2-C2B10H10)P d (P Et3)-
Cl (13). To a stirred toluene solution (15 mL) of 12a (0.1 g,
0.81 mmol) was added PEt3 (0.25 mL, 1 M, 0.25 mmol) at room
temperature, and the mixture was stirred for 8 h. After
filtering through Celite, the solvent was removed in vacuo and
the residue was recrystallized from toluene/hexane to afford
complex 13 as a colorless crystalline solid (88% yield), mp 176-
Hz, Sn-C). 31P NMR (CDCl3): δ 35.22 (s, J
) 55.2 Hz,
1
31
119
P- Sn
PPh2). 119Sn NMR (CDCl3): δ -30.2 (d, J
) 320.3 Hz).
1
119
31
Sn-
P
Anal. Calcd for C17H28B10BrPSn: C, 35.83; H, 4.91. Found: C,
35.48; H, 4.78.
1,2-Bis(1-d ip h e n ylp h osp h in o-1,2-ca r b or a n e )t e t r a -
m eth yld ista n n a n e (10). To a stirred toluene solution (20 mL)
of 2a (0.15 g, 0.27 mmol) was added an excess of sodium (0.031
g, 1.35 mmol) at room temperature, and the mixture was
stirred for 3 h. After filtering through Celite, the solution was
concentrated under reduced pressure to incipient crystalliza-
tion and stored in a freezer at ca. -10 to -15 °C to give 10 as
colorless crystals. Yield: 46%, mp 290 °C. 1H NMR (CDCl3,
1
179 °C. H NMR (CDCl3, 25 °C): δ 8.07-7.44 (m, 10H, PPh2),
3.76 (m, 6H, CH2), 1.25-1.36 (m, 9H, CH3). 0.59 (s, 6H,
2
) 51.6 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 136.39,
119
J H-
Sn
136.19, 132.10, 129.22, 128.28, 128.13, (Ph), 16.86 (s, CH2),
9.18 (s, CH3), -1.33 (s, Sn-C). 31P NMR (CDCl3): δ 80.49 (d,
2J P-P ) 428.8 Hz, PPh2), -94.53 (d, J P-P ) 428.8 Hz, PEt3).
2
2
119
25 °C): δ 7.66-7.25 (m, 20H, PPh2), 0.67 (s, 12H, J H-
)
)
Sn
Anal. Calcd for
C22H41B10ClP2PdSn: C, 35.91; H, 5.51.
2
3
3
117
119
117
121.5 Hz, J H-
) 74.7 Hz, J H-
) 26.4 Hz, J H-
Sn
Sn
Sn
Found: C, 36.14; H, 5.62.
18.3 Hz, Sn-CH3). 13C{1H} NMR (CDCl3): δ 135.59, 135.06,
134.00, 134.55, 131.29, 129.08, 128.89, 128.54, 128.06, 127.58
(Ph),. 3.13 (s, Sn-C). 31P NMR (CDCl3): δ -12.78 (s, PPh2).
119Sn NMR (CDCl3): δ 162.6. Anal. Calcd for C32H52B20P2Sn2:
C, 40.37; H, 5.46. Found: C, 39.96; H, 5.24.
X-r a y Cr ysta llogr a p h y. Details of the crystal data and a
summary of intensity data collection parameters for 9b, 11,
and 13 are given in Table 1. Crystals of 9b and 11 were grown
from toluene, and a crystal of 13 was grown from toluene/
hexane stored at -10 to -20 °C. Crystals of 9b, 11, and 13
were mounted in thin-walled glass capillaries and sealed under
argon. The data sets for the three crystals were collected on
an Enrf CAD 4 automated diffractometer. Mo KR radiation (λ
) 0.7107 Å) was used for all structures. Each structure was
solved by the application of direct methods using the SHELX-
96 program and least-squares refinement using SHELXL-97.
All non-hydrogen atoms in compounds 9b, 11, and 13 were
refined anisotropically. All other hydrogen atoms were in-
cluded in the calculated positions.
P r ep a r a tion of P d (1-P P h 2-2-Sn Me2-1,2-C2B10H10)2 (11).
To a stirred toluene solution (15 mL) of 10 (0.1 g, 0.105 mmol)
was added Pd2(dba)3 (0.08 g, 0.087 mmol) dissolved in toluene
(5 mL) at room temperature, and the mixture was stirred for
3 h at that temperature. The solvent was removed in vacuo
and chromatographed using CH2Cl2 and hexane (1:1) as eluent
(Rf ) 0.58). The first band was crystallized from CH2Cl2/hexane
at -15 °C to give 11 as white crystals in 34% yield, mp 198-
201 °C. 1H NMR (CDCl3, 25 °C): δ 7.38-7.06 (m, 20H, PPh2),
2
0.48 (s, 12H, J H-Sn ) 64.3 Hz, Sn-CH3). 13C{1H} NMR
(CDCl3): δ 134.81, 134.64, 134.05, 131.61, 131.24, 129.62,
128.86, 128.34, 128.06, 127.45 (Ph), 2.85 (s, Sn-C). 31P NMR
Ack n ow led gm en t. We are grateful to Korea Uni-
versity (1996, J .K.) and CRM-KOSEF (H.J .) for the
generous financial support. Financial support from the
Brain Korea 21 program is gratefully acknowledged.
(CDCl3): δ 78.60 (d, 2J P- Sn(trans) ) 2054.8 Hz, 2J P-
)
119
117
Sn(trans)
2
2
119
117
1943.0 Hz, J P-
) 207.7 Hz, J P-
) 194.2 Hz,
) 1284.2 Hz,
Sn(cis)
Sn(cis)
2
PPh2). 119Sn NMR (CDCl3): δ 166.1 (d, J
119
31
Sn-
P
2
117
31
Sn-
J
) 144.2 Hz). Anal. Calcd for C32H52B20P2PdSn2: C,
36.31; H, 4.91. Found: C, 36.02; H, 4.71.
P
Su p p or tin g In for m a tion Ava ila ble: Tables listing crys-
tallographic information, atomic coordinates and Beq values,
anistropic thermal parameters, and intramolecular bond
distances, angles, and torsion angles for 9b, 11 and 13. This
material is available free of charge via the Internet at
http://pubs.acs.org.
P r ep a r a t ion of [(1-P P h 2-2-Sn Me2-1,2-C2B10H 10)P d (µ-
Cl)]2 (12a ). To a stirred toluene solution (20 mL) of 2a (0.15
g, 0.207 mmol) was added Pd2(dba)3 (0.095 g, 0.104 mmol) at
room temperature, and the mixture was stirred for 2 h. After
filtering through Celite, the solvent was removed in vacuo. The
reaction mixture was washed with hexane (15 mL × 3). The
residue was extracted with 25 mL of toluene. The volume of
OM0007872