Insertion of Elemental Sulfur and SO2 into the Metal-Hydride and Metal-Carbon Bonds of Platinum Compounds

Article abstract of DOI:10.1021/om980772s

Elemental sulfur (S₈) has been found to insert only one sulfur atom into the metal-hydride bonds of the platinum alkyl and aryl hydride complexes [(dcpe)PtRH] (dcpe = Cy₂PC₂H₄-PCy₂). Unlike the parent compounds, the S-inserted complexes do not undergo reductive elimination to form the corresponding alkane- or arenethiols. Methane is lost from the methyl sulfhydryl complex. Sulfur dioxide was also found to insert into a platinum-methyl bond to form the corresponding S-bound sulfinate, which upon reacting with mineral acids generates methylsulfinic acid.

Full text of DOI:10.1021/om980772s

Organometallics 1999, 18, 227-234
227
In ser tion of Elem en ta l Su lfu r a n d SO2 in to th e
Meta l-Hyd r id e a n d Meta l-Ca r bon Bon d s of P la tin u m
Com p ou n d s
Michael S. Morton, Rene J . Lachicotte, David A. Vicic, and William D. J ones*
Department of Chemistry, University of Rochester, Rochester, New York 14627
Received September 15, 1998
Elemental sulfur (S8) has been found to insert only one sulfur atom into the metal-hydride
bonds of the platinum alkyl and aryl hydride complexes [(dcpe)PtRH] (dcpe ) Cy2PC2H4-
PCy2). Unlike the parent compounds, the S-inserted complexes do not undergo reductive
elimination to form the corresponding alkane- or arenethiols. Methane is lost from the methyl
sulfhydryl complex. Sulfur dioxide was also found to insert into a platinum-methyl bond to
form the corresponding S-bound sulfinate, which upon reacting with mineral acids generates
methylsulfinic acid.
In tr od u ction
the insertion of SO2 into group 8 metal-carbon bonds.8
In this paper, similar insertions of SO2 into the M-C
bonds of group 10 metal complexes are reported. We
have also been able to show that it is possible to release
the RSO2 group from the metal to form methylsulfinic
acid.
The selective activation and transformation of C-H
bonds has been a major driving force behind much
current research in organometallic chemistry.1 In 1986,
Whitesides was able to develop a platinum-based system
that was able to selectively activate C-H bonds in
alkanes and arenes by the oxidative addition of the C-H
bond to the coordinatively unsaturated [(dcpe)Pt0] (dcpe
) Cy2PC2H4PCy2) species.2,3 This paper explores the
potential use of this chemistry to develop a way of
activating methane and other alkyl and aryl compounds,
followed by insertion of sulfur-bearing species to syn-
thesize sulfur-bearing organic compounds.
Resu lts a n d Discu ssion
Syn th esis of Su lfu r In ser tion Ad d u cts. Addition
of elemental sulfur (S8) to a benzene or THF solution of
t
Pt(dcpe)(R)H (R ) Me, CH2 Bu, Ph) leads to the quan-
titative formation of the new products Pt(dcpe)(R)(SH)
t
(R ) Me (1), CH2 Bu (2), Ph (3)). NMR spectroscopy
proved to be ideal for following the progress of these
reactions. For example, addition of elemental sulfur (S8)
to a THF-d8 solution of Pt(dcpe)(Me)H led to complete
One convenient sulfur source capable of insertion
chemistry is elemental sulfur (S8). While rare, there are
a few reported cases of elemental sulfur insertion into
transition-metal-ligand bonds.4,6 Early work by Legz-
dins showed an example of insertion of a single sulfur
atom from elemental sulfur into a metal-carbon bond.6
A recent report by Hillhouse demonstrated the facile
insertion of sulfur into the metal-aryl bond in a (bipy)-
Ni(aryl)(alkyl) complex.7 All other examples of using
elemental sulfur resulted in a sulfur-chain fragment (Sx)
being inserted.
1
reaction within 5 min. The H NMR spectrum showed
that the methyl resonance of Pt(dcpe)(Me)H at δ 0.67
(dd, J PtH ) 70 Hz) had shifted upfield to δ 0.36 (dd, J PtH
) 62 Hz). A more dramatic change was seen in the
hydride resonance, which shifted downfield from the
signal for the starting material at δ -0.445 (dd, J PtH
)
1150 Hz) to δ -0.917 (dd, J PtH ) 62 Hz) with a large
change in the Pt-H coupling constant. 31P NMR spec-
troscopy provided another handle for monitoring the
reaction. The 31P NMR spectrum of 1 in THF-d8 displays
a resonance at δ 62.33 (s, J PtP ) 3064 Hz), which cor-
responds to the phosphorus trans to the SH group. This
large Pt-P coupling constant is seen in other complexes
of phosphorus groups trans to either halides or main-
group metals.2,3 A second resonance is seen in the 31P
NMR spectrum at δ 67.02 (J PtP ) 1811 Hz) with a Pt-P
coupling constant similar to those seen for the starting
materials. Curiously, no P-P coupling is observed.
1 decomposes in solution in the presence of excess S8.
Another synthetic route was devised to allow for com-
plete characterization which also allowed for the elimi-
nation of problems involving removal of unreacted S8
In this paper, three new compounds are presented
that are able to cleanly insert one sulfur atom into their
M-H bonds. All three examples are based on the group
10 metal system studied by Whitesides. The reactivity
of these species is also presented. We recently reported
(1) Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H.
Acc. Chem. Res. 1995, 28, 154-162.
(2) Hackett, M.; Ibers, J . A.; J ernakoff, P.; Whitesides, G. M. J . Am.
Chem. Soc. 1986, 108, 8094-8095.
(3) Hackett, M.; Whitesides, G. M. J . Am. Chem. Soc. 1988, 110,
1449-1462.
(4) Giannotti, C.; Fontaine, C.; Septe, B.; Doue, D. J . Organomet.
Chem. 1972, 39, C74-C78.
(5) Giannotti, C.; Merle, G. J . Organomet. Chem. 1976, 113, 45-
56.
(6) Legzdins, P.; Sanchez, L. J . Am. Chem. Soc. 1985, 107, 5525-
5526.
(7) Han, R.; Hillhouse, G. L. J . Am. Chem. Soc. 1998, 120, 7657-
7658.
(8) Lefort, L.; Lachicotte, R. J .; J ones, W. D. Organometallics 1998,
17, 1420-1425.
10.1021/om980772s CCC: $18.00 © 1999 American Chemical Society
Publication on Web 12/29/1998

228 Organometallics, Vol. 18, No. 2, 1999
Morton et al.
in the samples. The nucleophilic attack of SH- (from
NaSH) on the metal alkyl or aryl halides was used to
generate large quantities of 1 cleanly (eq 1). Crystals
F igu r e 1. ORTEP drawing of [Pt(Cy2PC2H4PCy2)-
t
(CH2 Bu)(SH)] (2). Ellipsoids are shown at the 30% level.
of 1 were obtained by cooling a supersaturated hot
acetone solution. Both the methyl and the sulfhydryl
groups were sufficiently disordered to prevent a satis-
factory X-ray structure of 1 from being obtained, but
the model indicated that only a single sulfur atom had
inserted into the M-H bond.
ture (Figure 2) shows that only one S atom insertion
has occurred into the M-H bond. Crystallographic data
are listed in Table 1, and selected distances and angles
are given in Table 2.
For comparison, the methylene-bridged chelating
phosphine analogue of 1, [Pt(Cy2PCH2PCy2)(Me)(SH)]
(4) was synthesized by way of the NaSH route. The 31P
NMR spectrum of 4 showed large changes from those
of the ethylene-bridged compounds. The resonances of
4 are shifted ∼80 ppm upfield from those of 1, appearing
at δ -26.76 (J PP ) 43 Hz, J PtP ) 1376 Hz) and δ -28.36
(J PP ) 43 Hz, J PtP ) 2727 Hz). The P-P coupling can
now be seen, and each resonance appears as a doublet.
In compounds 1-3, the P-P coupling must be small and
is not observable in the NMR spectra.
Compounds 2 and 3, the CH2CMe3 and Ph deriva-
tives, were synthesized similarly. In the case of 2,
elemental sulfur was added to a THF-d8 solution of [Pt-
(dcpe)(CH2CMe3)H] and the reaction monitored by NMR
spectroscopy until all traces of the starting material
were consumed. The hydride resonance shifted down-
1
field in the H NMR spectrum to δ -0.457 (J PtH ) 61
Hz) upon sulfur insertion. Two resonances were ob-
served in the 31P NMR spectrum, one at δ 57.88 (J PtP
)
3210 Hz) assigned to the phosphorus trans to the SH
group and another at δ 64.07 (J PtP ) 1626 Hz) assigned
to the phosphorus trans to the neopentyl group. As in
the case of 1, compound 2 appears to be unstable in
solution with excess S8; therefore, the NaSH route was
used to generate larger quantities of 2 (eq 1).
Str u ctu r es of Com p lexes 2 a n d 3. Complexes 2 and
3 are structurally similar, except for the alkyl or aryl
group bound to the platinum center. In each case, they
consist of mononuclear neutral molecules (Figures 1 and
2) with no significant intermolecular interactions. The
platinum metal is coordinated to two phosphorus atoms,
one carbon atom, and one sulfur atom in a slightly
distorted square planar geometry.
Crystals of 2 were obtained by layering a solution of
2 in methylene chloride with hexanes. The X-ray
structure (Figure 1) shows that insertion of a single
sulfur atom has occurred into the M-H bond. Crystal-
lographic data are listed in Table 1, and selected
distances and angles are given in Table 2.
The three X-ray structures of 1-3 definitively prove
that only one sulfur atom was inserted into the Pt-H
bonds. Of the previously reported cases of elemental
sulfur insertions, only the studies by Legzdins6 and
Hillhouse7 showed single-sulfur-atom insertions. In the
case of the W-C insertion, a mechanism was proposed
to explain the observation of single-atom insertion, in
which it was proposed that the tungsten species first
coordinated with the S8 and the bound S atom then
underwent intramolecular nucleophilic attack by an
alkyl group with concomitant expulsion of the residual
sulfur fragment (eq 2). It was also found that the
The platinum phenyl sulfhydryl complex 3 was syn-
thesized by addition of elemental sulfur (S8) to a C6D6
solution of Pt(dcpe)(Ph)H. The hydride resonance in the
1H NMR spectrum shifted downfield to δ 0.168 (J PtH
)
65 Hz) following sulfur insertion. Two resonances were
observed in the 31P NMR spectrum at δ 54.58 (J PtP
)
3025 Hz) for the phosphorus trans to the SH group, and
at δ 60.55 (J PtP ) 1720 Hz) for the phosphorus trans to
the phenyl group. Unlike the cases of 1 and 2, the
reaction with S8 was slower in the case of 3, taking up
to 2 h to consume all of the starting material. The
platinum phenyl sulfhydryl complex 3 also appears to
be more stable in solution with excess S8. Nevertheless,
an alternate synthetic route was used to obtain pure,
S8-free samples of 3.
Crystals of 3 were obtained by layering a solution of
3 in methylene chloride with hexane. The X-ray struc-

Insertion into M-H and M-C Bonds of Pt Compounds
Organometallics, Vol. 18, No. 2, 1999 229
Ta ble 1. Su m m a r y of Cr ysta llogr a p h ic Da ta for Com p lexes 2, 3, a n d 7
2
3
7
Crystal Parameters
35H68OP2PtS
793.98
chem formula
fw
C
C35H60OP2PtS
785.92
C47H77ClN2O2Pt
932.65
cryst syst
space group (No.)
Z
monoclinic
C2/c (15)
16
monoclinic
P21/n (14)
4
orthorhombic
Pca21 (29)
4
a, Å
b, Å
c, Å
â, deg
V, Å3
46.3269(6)
17.0101(3)
20.4152(1)
112.334(1)
14880.9(3)
1.418
10.7275(2)
22.1317(4)
15.3769(2)
102.330(1)
3566.5(1)
1.464
18.4367(2)
10.6432(1)
17.2377(1)
90
3387.43(5)
1.562
F
calcd, g cm-3
cryst dimens, mm3
temp, °C
0.20 × 0.22 × 0.38
0.20 × 0.30 × 0.40
0.05 × 0.20 × 0.20
-80
-80
-80
Measurement of Intensity Data and Refinement Parameters
radiation (λ, Å)
2θ range, deg
Mo KR (0.710 73)
3-47
3-56
4-56
19 069
7612
6.32, 9.74
5870
total no. of data
no. of unique data
30 939
10 536
3.48, 4.09
8679
20 776
8245
4.21, 6.24
6690
354
4.108
empirical (SADABS)
0.708-0.928
R
int, Rσ (%)a
no. of obsd data (I > 2σ(I))
no. of params varied
µ, mm-1
677
3.938
314
4.480
abs cor
range of transmissn factors
Flack param
0.648-0.928
0.783-0.928
0.011(9)
GOF
1.037
3.32, 6.94
4.66, 7.39
1.178
5.46, 8.21
7.56, 8.78
1.086
6.07, 8.45
8.86, 9.24
R1(Fo), wR2(Fo) obsd (%)
2
R1(Fo), wR2(Fo) all (%)
2
Rint ) ∑|Fo2 - F2(mean)|/∑[F2], and Rσ ) ∑[σ(F2)]/∑[F2], where w ) 1/[σ2(F2) + (aP)2 + bP] and P ) [(Max;0,Fo2) + 2F2o]/3.
a
o
o
o
o
o
Ta ble 2. Selected Dista n ces (Å) a n d An gles (d eg)
for P t(d cp e)(CH2tBu )(SH) (2), P t(d cp e)(P h )(SH) (3),
a n d P t(d cp e)(SO2Me)Me (7)
2a
3
7
Distances
Pt1-P1
Pt1-P2
Pt1-C27
Pt1-S1
2.232(3)
2.282(3)
2.141(11)
2.336(4)
2.291(2)
2.242(2)
2.075(6)
2.339(2)
2.316(2)
2.266(2)
2.136(8)
2.335(2)
Angles
P1-Pt1-P2
S1-Pt1-C27
P1-Pt1-S1
P1-Pt1-C27
P2-Pt1-S1
P2-Pt1-C27
86.8(1)
88.2(9)
172.0(9)
92.2(5)
92.8(12)
178.3(4)
87.43(5)
86.7(2)
93.74(6)
179.6(2)
178.62(6)
92.1(2)
86.74(9)
90.5(2)
90.91(8)
177.5(2)
172.67(8)
91.6 (2)
a
Values listed are for the average of two independent molec-
ules.
tungsten species was able to further react with more
elemental sulfur. Unlike the previous tungsten case, we
saw no indication of sulfur insertion into the Pt-C
bonds.
The Pt-S bond lengths in 2 and 3 are similar to those
previously reported in the literature (Chart 1). They are
similar to other terminally bound sulfur groups such
as Pt(PPh3)2(SH)2 (A; Pt-S ) 2.360(2) Å),9 Pt(dppe)-
(SC5H4N)2 (B; Pt-S ) 2.358(1) Å),10 and cis-{Pt(SCH2-
Ph)(µ-SCH2Ph)(PMePh2)}2 (C; Pt-Sterminal ) 2.342(5)
Å).11 They are also similar but slightly shorter than
those seen in bridging sulfur groups such as cis-{Pt-
(SCH2Ph)(µ-SCH2Ph)(PMePh2)}2 (C; Pt-Sbridging ) 2.380
F igu r e 2. ORTEP drawing of [Pt(Cy2PC2H4PCy2)(Ph)-
(SH)] (3). Ellipsoids are shown at the 30% level.
Å),11 [Pt2(µ-S)(SCH2Ph)2(µ-dppm)2] (D; Pt-Sbridging
)
2.347(3) Å),12 [{Pt(Me)2(µ-S(Et)2)}2] (E; Pt-S ) 2.356-
(3) Å),13 and the mixed-oxidation-state complex [{Pt-
(dppe)}(µ-SMe)2{Pt(Me)3Cl}] (F ; PtII-S ) 2.386 (4) Å,
PtIV-S ) 2.468(4) Å).14 The Pt-S bond lengths are also
longer than those seen in sulfur groups bound to the
other group 10 metals, such as in the palladium species
trans-[Pd(PiBu3)2(SH)2] (G; Pd-S ) 2.305(1) Å),15 and
(12) Hadj-Bagheri, N.; Puddephatt, R. J . J . Chem. Soc., Dalton
Trans. 1990, 535-540.
(13) Bancroft, D. P.; Cotton, F. A.; Falvello, L. R.; Schwotzer, W.
Inorg. Chem. 1986, 25, 763-770.
(9) Briant, C. E.; Hughes, G. R.; Minshall, P. C.; Mingos, D. M. P.
J . Organomet. Chem. 1980, 202.
(10) Capdevila, M.; Clegg, W.; Gonzalez-Duarte, P.; Harris, B.; Mira,
I.; Sola, J .; Taylor, I. C. J . Chem. Soc., Dalton Trans. 1992.
(11) Bird, P. H.; Siriwardane, U.; Lai, R. D.; Shaver, A. Can. J .
Chem. 1982, 60, 2075-2081.
(14) Abel, E. W.; Cooley, N. A.; Kite, K.; Orrell, K. G.; Sik, V.;
Hursthouse, M. B.; Dawes, H. M. Polyhedron 1987, 6, 1261-1272.
(15) Ghilardi, C. A.; Midollini, S.; Nuzzi, F.; Orlandini, A. Transition
Met. Chem. 1983, 8, 73-75.

230 Organometallics, Vol. 18, No. 2, 1999
Morton et al.
Ch a r t 1
To see if a palladium species might be more reactive
toward reductive elimination, the corresponding com-
plex Pd(dcpe)(Me)(SH) (5) was synthesized from the
reaction of Pd(dmpe)(Me)Cl and NaSH. This compound
was found to be more thermally labile, as expected, but
as with the platinum case only CH4 was seen to
eliminate at 80 °C in THF-d8.
The sulfur-inserted species were seen to be reactive
toward both mineral acids and halogens. 1 reacted with
aqueous HCl to form Pt(dcpe)(Me)Cl with the loss of H2S
and ultimately Pt(dcpe)Cl2 with the additional loss of
CH4 (eq 3). 1 also reacted rapidly with I2 and Br2. The
much longer than those seen for the two nickel species
H (Ni-S ) 2.256(11) Å16) and I (Ni-S ) 2.188(3) Å17).
The Pt-P bond lengths are also comparable to those of
previously reported compounds, with the Pt-P bound
trans to the SH group being longer then those of the
Pt-P bond cis to the SH group.18
The bond angles around the Pt atoms in complexes 2
and 3 range between 86.7 and 93.7°, with both the
P-Pt-P and the S-Pt-C angles being similar. The
largest angular deviation from square planar in the
complex is between the phosphorus atoms and the alkyl/
aryl group or the sulfur atom, indicating that the bulk
of the alkyl or aryl group has little effect on the
geometry around the metal center.
addition of solid I2 to a solution of 1 in CD2Cl2 converted
all of 1 quantitatively to Pt(dcpe)I2, as determined by
NMR spectroscopy. When a solution of 1 in CD2Cl2 was
reacted with Br2, the reaction was much slower, allow-
ing for the observance of the PtIV intermediate that must
also be formed in the I2 reaction. The PtIV species then
converts to form [Pt(Cy2PC2H4PCy2)Br2], as determined
by NMR spectroscopy and compared to known samples
(eq 4). In both cases, there was no evidence in the NMR
spectra for formation of MeSH upon generation of the
dihalide species.
Rea ctivity of th e Su lfu r -In ser ted Sp ecies. One of
the major reasons for studying the insertion of S into
Pt-H bonds was the desire of finding a system that
could activate methane, derivatize the methyl group
through sulfur insertion, and finally reductively elimi-
nate the derivatized methyl compound. All attempts to
induce 1 to reductively eliminate methanethiol ther-
mally failed. At 130 °C, methane was lost but no
evidence for the formation of MeSH could be seen by
The reaction of MeI was also investigated, since
similar reactions of PtII species to form the correspond-
ing PtIV species are known in the literature.20,21 MeI was
reacted with a solution of 1 in CD2Cl2. After 20 h, all 1
had been quantitatively converted to Pt(dcpe)I2. As in
the cases of reactions with the halogens, no NMR
evidence was seen to indicate the formation of MeSH
or Me2S.
In an attempt to see how stable these systems were
toward other sulfur sources, 1 was reacted with H2S.
When a sample of 1 was dissolved in C6D6 and then
sealed under 1 atm of H2S, 1 was completely converted
to Pt(dcpe)(SH)2 (6), with the loss of CH4. An alternate
synthetic route to this product was discovered using the
nucleophilic reactivity of SH- toward the metal dihalide
to confirm the generation of Pt(dcpe)(SH)2.
1
NMR spectroscopy. As the reaction proceeded, the H
NMR spectrum showed the disappearance of resonances
corresponding to both the methyl and the SH groups,
while the 31P NMR spectrum showed the formation of
a singlet for a new symmetric chelating-phosphine-
containing species. On the basis of analytical data, this
complex is assigned as the sulfur-bridged dimer [Pt-
(dcpe)(µ-S)]2. The lack of reductive elimination of the
C-S bond in this system stands in contrast to the nickel
system studied by Hillhouse, which eliminated C-S
bonds readily.7 Hartwig has also seen facile reductive
elimination of C-S bonds in (diphos)Pd(Ar)(SR) com-
pounds.19
(16) Di Vaira, M.; Midollini, S.; Sacconi, L. Inorg. Chem. 1977, 16,
1518-1524.
When a solution of 1 in THF-d8 was exposed to near-
UV light from a Xe/Hg lamp, the system decomposed.
(17) Di Vaira, M.; Midollini, S.; Sacconi, L. Inorg. Chem. 1978, 17,
816-819.
(18) Capdevila, M.; Gonzalez-Duarte, P.; Mira, I.; Sola, J .; Clegg,
W. Polyhedron 1992, 11, 3091-3093.
(20) Goldberg, K. I.; Yan, J .; Winter, E. L. J . Am. Chem. Soc. 1994,
116, 1573-1574.
(21) Goldberg, K. I.; Yan, J .; Breitung, E. M. J . Am. Chem. Soc.
1995, 117, 6889-6896.
(19) Baran˜ano, D.; Hartwig, J . F. J . Am. Chem. Soc. 1991, 117,
2937-2938. Mann, G.; Baran˜ano, D.; Hartwig, J . F., Rheingold, A. L.;
Guzei, I. A. J . Am. Chem. Soc. 1998, 120, 9205-9219.

Insertion into M-H and M-C Bonds of Pt Compounds
Organometallics, Vol. 18, No. 2, 1999 231
sumably, the SO2 inserts into the Pt-C bond of Pt(dcpe)-
(Me)Cl, but the product then rapidly disproportionates
with any remaining starting material to form the 1:1
mixture of observed products. Failure to induce Pt-
(dcpe)(Me)Cl to disproportionate with itself at elevated
temperatures lends support for the SO2 insertion being
necessary prior to disproportionation.
F igu r e 3. ORTEP drawing of [Pt(Cy2PC2H4PCy2)(SO2Me)-
Me] (7). Ellipsoids are shown at the 30% level.
1H NMR spectroscopy provided evidence for the forma-
tion of a small quantity of CH4, but no MeSH was
observed.
Attempts to synthesize the phenyl analogue of 7 have
failed to yield the phenylsulfinate species. Addition of
1 atm of SO2 to a solution of Pt(dcpe)Ph2 (8) failed to
produce any new products. This may be caused by the
increased bulk of a phenyl group relative to a methyl
group and the increased Pt-C bond strength in the Pt-
Ph compound vs the Pt-Me compound.22
SO2 In ser tion in to P t-C Bon d s. Addition of 1 atm
of SO2 to a solution of Pt(dcpe)(Me)2 in THF-d8 leads to
the quantitative formation (on the basis of NMR) of the
new product 7 after 20 h at ambient temperature (eq
5). The clear solution does not change color during the
It had been reported that mineral acids are able to
react with metal-sulfinate groups to give the corre-
sponding sulfinic acids.8 When 12 M HCl(aq) was added
to a sample of 7, both methylsulfinic acid and methane
were formed along with [Pt(Cy2PC2H4PCy2)Cl2], as
determined by 1H and 31P spectra. An authentic sample
of methylsulfinic acid was synthesized from the com-
1
mercially available Na salt, and the H NMR spectrum
matched that seen in the reaction with HCl.
course of the reaction, and no intermediates can be seen
while monitoring the reaction by NMR spectroscopy.
The 1H NMR spectrum of the product, Pt(dcpe)(SO2Me)-
Me (7), exhibits one methyl resonance (δ 0.557) in a
location similar to that of the starting material. The
other methyl resonance corresponding to the SO2-
inserted methyl is masked by resonances of the chelat-
ing phosphine ligand. Two singlet resonances are ob-
served in the 31P NMR spectrum at δ 53.36 (J PtP ) 2499
Hz) and δ 71.73 (J PtP ) 1919 Hz). As seen with the
sulfur-inserted compounds, there is both a large and a
small Pt-P coupling constant, with the phosphorus
atom trans to the sulfinate group having the larger
Pt-P coupling.
Crystals of 7 were obtained by layering a methylene
chloride solution with hexanes. The X-ray structure
(Figure 3) shows that SO2 insertion has occurred into
the Pt-C bond in a [1,1] fashion, giving an S-sulfinate
(eq 5). Crystallographic data are listed in Table 1, and
selected distances and angles are given in Table 2.
Con clu sion
Three new transition-metal compounds have been
found to undergo a clean sulfur insertion into their
M-H bonds. In each case, the sulfur atom, from
elemental sulfur, reacts with the metal systems quan-
titatively under mild conditions. Alternate synthetic
routes utilizing the nucleophilic addition of SH- have
been developed in order to allow complete characteriza-
tion of these S-inserted species. In none of the cases does
reductive elimination of an arene- or alkanethiol occur.
The platinum sulfhydryl compounds were shown to be
reactive toward mineral acids and halogens. Also, a new
transition-metal compound has been found to undergo
a clean SO2 insertion into its M-C bond. This insertion
proceeds quantitatively under mild conditions. Meth-
ylsulfinic acid has been shown to form upon reactions
of mineral acids with the SO2-inserted species.
Previously, we reported that SO2 is capable of insert-
ing into group 8 metal-carbon bonds in Cp*Rh(PMe3)-
(R)Cl (R ) Me, Ph).8 Addition of 1 atm of SO2 to a
solution of Pt(dcpe)(Me)Cl did not result in the expected
Pt(dcpe)(SO2Me)Cl but instead resulted in a 1:1 ratio
of Pt(dcpe)(SO2Me)Me (7) and Pt(dcpe)Cl2 (eq 6). Pre-
Exp er im en ta l Section
Gen er a l Con sid er a tion s. All manipulations were per-
formed under an N2 atmosphere, either on a high-vacuum line
(22) Simo˜es, J . A. M.; Beauchamp, J . L. Chem. Rev. 1990, 90, 629-
688.

232 Organometallics, Vol. 18, No. 2, 1999
Morton et al.
using modified Schlenk techniques or in a Vacuum Atmo-
spheres Corp. glovebox. Tetrahydrofuran and benzene were
distilled from sodium-benzophenone ketyl under N2. Dichlo-
romethane was distilled from CaH2. Alkane solvents were
made olefin-free by stirring over H2SO4, washing with aqueous
KMnO4 and water, and distilling from sodium-benzophenone
cis-Su lfh yd r yln eop en tyl[bis(d icycloh exylp h osp h in o)-
eth a n e]p la tin u m (II) (2). Meth od A. To a solution of 25 mg
(0.035 mmol) of Pt(dcpe)(CH2 Bu)Cl in about 0.5 mL of dry
t
THF-d8 was added 2.2 mg (0.039 mmol) of NaSH. The resulting
yellow solution was stirred at ambient temperature for 15 h,
resulting in an orange-tan solution that was evaporated; the
residue was then extracted with H2O and CH2Cl2. The organic
layers were combined, dried over MgSO4, and evaporated to
dryness on a rotary evaporator to yield a tan solid. Recrystal-
lization from a CH2Cl2 solution layered with hexanes yielded
ketyl under N2. Dichloromethane-d2, benzene-d6, p-xylene-d10
,
and tetrahydrofuran-d8 were purchased from Cambridge
Isotope Laboratories, dried over either CaH2 (in the case of
CD2Cl2) or sodium-benzophenone ketyl, distilled under vacuum,
and stored in ampules with Teflon-sealed vacuum line adapt-
ers. The preparations of Pt(dcpe)(Me)H,3 Pt(dcpe)(Me)Cl,3 Pt-
t
white crystals of Pt(dcpe)(CH2 Bu)(SH) (2; 56 mg, 73%). 1H
NMR (THF-d8): δ -0.457 (dd, J PH ) 6, 16 Hz, J PtH ) 61 Hz,
1 H, SH), 1.095 (s, 15 H, t-Bu), 1.2-2.6 (m, 50 H, Cy2PC2H4-
PCy2 and CH2). 31P NMR (THF-d8): δ 57.88 (s, J PtP ) 3210
Hz), 64.07 (s, J PtP ) 1626 Hz). Anal. Calcd for C31H60P2PtS‚
1/2CH2Cl2: C, 49.50; H, 8.04. Found: C, 49.46; H, 8.31.
Met h od B. A 14 mg (0.02 mmol) amount of Pt(dcpe)-
t
t
(dcpe)(CH2 Bu)Cl,23 Pt(dcpe)(CH2 Bu)H,23 Pt(dcpe)(Ph)H,23 Pt-
(dcpe)(Ph)Cl,23 Pt(dcpe)Cl2,3 Pt(dcpe)I2,24 Pt(dcpe)Br2,25 Pt(dcpe)-
(Me)2,26 and Pd(cod)(Me)Cl27 have been previously reported.
NaSH was purchased from Alfa. S8, MeI, Br2, and I2 were
purchased from Aldrich Chemical Co. and used without further
purification.
t
(CH2 Bu)H and 2.0 mg (0.03 mmol) of S8 were added to an
All 1H NMR and 31P NMR spectra were recorded on a
Bruker AMX400 spectrometer. All 1H chemical shifts are
reported in ppm (δ) relative to tetramethylsilane and refer-
enced using the chemical shifts of residual solvent resonances
(C6H6, δ 7.15; THF, δ 3.58; CH2Cl2, δ 5.32; p-xylene, δ 7.22).
31P NMR spectra were referenced to external 30% H3PO4 (δ
0.0). Unless otherwise noted, all NMR-scale reactions were
carried out in NMR tubes equipped with Teflon seals and
connected to a high-vacuum line. Any solvents used were then
vacuum-transferred into the tube and then resealed. Analyses
were obtained from Desert Analytics. A Siemens SMART CCD
area detector diffractometer equipped with an LT-2 low-
temperature unit was used for X-ray crystal structure deter-
mination.
NMR tube and dissolved in about 1 mL of dry, oxygen-free
THF-d8. The resulting yellow solution was mixed at ambient
temperature for 1 h, at which time the material had quanti-
tatively converted to Pt(dcpe)(CH2 Bu)(SH) (2), as determined
by NMR spectroscopy.
t
cis-Su lfh yd r ylp h e n yl[b is(d icycloh e xylp h osp h in o)-
eth a n e]p la tin u m (II) (3). Meth od A. To a solution of 101 mg
(0.14 mmol) of Pt(dcpe)(Ph)Cl in 6 mL of THF was added 16
mg (0.30 mmol) of NaSH. The solution was stirred at ambient
temperature for 2 h, resulting in a yellow solution. The solution
was evaporated and the residue extracted with H2O and CH2-
Cl2. All organic layers were combined, dried with MgSO4, and
evaporated to dryness on a rotary evaporator to yield a tan
solid. Recrystallization from a CH2Cl2 solution layered with
hexanes yielded amber crystals of Pt(dcpe)(Ph)(SH) (3; 68 mg,
cis-Su lfh yd r ylm e t h yl[b is(d icycloh e xylp h osp h in o)-
eth a n e]p la tin u m (II) (1). Meth od A. To a solution of 100 mg
(0.150 mmol) of Pt(dcpe)(Me)Cl in about 6 mL of dry THF was
added 3.4 mg (0.63 mmol) of NaSH. The resulting yellow
solution was stirred at ambient temperature for 15 h, resulting
in an orange-tan solution that was evaporated to dryness. The
residue was extracted with H2O and CH2Cl2. The organic
layers were combined, dried over MgSO4, and evaporated to
dryness on a rotary evaporator to yield a tan solid. Recrystal-
lization from a CH2Cl2 solution layered with hexanes yielded
1
68%). H NMR (C6D6): δ 0.168 (dd, J PH ) 6, 16 Hz; J PtH ) 65
Hz, 1 H, SH), 0.8-2.5 (m, 48 H, Cy2PC2H4PCy2), 7.03 (t, J PH
) 7 Hz, 1 H, Ph), 7.26 (t, J PH ) 7 Hz, 2 H, Ph), 7.80 (t, J PH
)
6 Hz, J PtH ) 46 Hz, 2 H, Ph). 31P NMR (C6D6): δ 54.58 (s, J PtP
) 3025 Hz), 60.55 (s, J PtP ) 1720 Hz). Anal. Calcd for C32H54P2-
PtS‚CH2Cl2: C, 48.77; H, 6.94. Found: C, 48.70; H, 7.13.
Meth od B. A 25 mg (0.036 mmol) amount of Pt(dcpe)(Ph)H
and a 4.0 mg (0.016 mmol) amount of S8 was added to an NMR
tube and dissolved in about 1 mL of dry, oxygen-free C6D6.
The resulting yellow solution was mixed at ambient temper-
ature for 2 h, at which time the material had quantitatively
converted to Pt(dcpe)(Ph)(SH) (3), as determined by NMR
spectroscopy.
1
white crystals of Pt(dcpe)(Me)(SH) (1; 93 mg, 93%). H NMR
(THF-d8): δ -0.917 (dd, J PH ) 6, 15 Hz, J PtH ) 62 Hz, 1 H,
SH), 0.361 (dd, J PH ) 5, 6 Hz, J PtH ) 62 Hz, 3 H, CH3), 1.2-
2.4 (m, 48 H, Cy2PC2H4PCy2). 1H NMR (C6D6): δ 0.195 (dd,
J PH ) 5, 16 Hz, J PtH ) 61 Hz, 3 H, CH3), 1.0-2.4 (m, 49 H,
Cy2PC2H4PCy2 and SH). 1H NMR (p-xylene-d10): δ -0.106 (dd,
J PH ) 6, 16 Hz, J PtH ) 62 Hz, 1 H, SH), 0.888 (dd, J PH ) 5, 6
Hz, J PtH ) 63 Hz, 3 H, CH3), 1.0-2.5 (m, 48 H, Cy2PC2H4-
PCy2). 31P NMR (THF-d8): δ 62.33 (s, J PtP ) 3064 Hz), 67.02
(s, J PtP ) 1811 Hz). 31P NMR (C6D6): δ 59.94 (s, J PtP ) 3070
Hz), 64.89 (s, J PtP ) 1800 Hz).). 31P NMR (p-xylene-d10): δ
64.98 (s, J PtP ) 3047 Hz), 70.01 (s, J PtP ) 1792 Hz). Anal. Calcd
for C27H52P2PtS: C, 48.71; H, 7.87. Found: C, 48.39; H, 7.67.
cis-Ch lor om eth yl[bis(dicycloh exylph osph in o)m eth an e]-
p la tin u m (II). To a solution of 150 mg (0.42 mmol) of Pt(COD)-
(Me)Cl in 5 mL of CH2Cl2 was added 175 mg (0.429 mmol) of
Cy2PCH2PCy2. The solution was stirred for 20 h, resulting in
a tan colored solution. The solution was concentrated to a tan
oil and washed with hexanes to remove residual cyclooctadi-
ene. Recrystallization from a CH2Cl2 solution layered with
hexanes yielded white crystals of Pt(Cy2PCH2PCy2)(Me)Cl (221
1
mg, 79.8%). H NMR (CD2Cl2) δ 0.388 (dd, J PH ) 6, 9 Hz, J PtH
) 59 Hz, 3 H, Me), 1.2-2.4 (m, 44 H, Cy2PCH2PCy2). 31P NMR
(CD2Cl2): δ -19.17 (d, J PP ) 42 Hz, J PtP ) 2799 Hz), -21.19
(d, J PP ) 42 Hz, J PtP ) 2799 Hz). Anal. Calcd for C26H49ClP2-
Pt‚CH2Cl2: C, 43.88; H, 6.96. Found: C, 44.13; H, 7.42.
cis-Su lfh yd r ylm e t h yl[b is(d icycloh e xylp h osp h in o)-
m eth a n e]p la tin u m (II) (4). A solution of 78 mg (0.12 mmol)
of Pt(Cy2PCH2PCy2)(Me)Cl in 6 mL of THF was treated with
14 mg (0.25 mmol) of NaSH and stirred at ambient temper-
ature for 15 h. The resulting orange-tan solution was evapo-
rated and the residue extracted with H2O and CH2Cl2. The
organic layers were combined, dried over MgSO4, and evapo-
rated to dryness on a rotary evaporator to yield a tan solid.
Recrystallization from a CH2Cl2 solution layered with hexanes
yielded white crystals of Pt(Cy2PCH2PCy2)(Me)(SH) (4; 56 mg,
Meth od B. A 14 mg (0.02 mmol) amount of Pt(dcpe)(Me)H
and 2.0 mg (0.03 mmol) of S8 were added to an NMR tube and
dissolved in about 1 mL of dry, oxygen-free THF-d8. The
resulting yellow solution was mixed at ambient temperature
1
for
/ h, at which time the material had quantitatively
2
converted to Pt(dcpe)(Me)(SH) (1), as determined by NMR
spectroscopy.
(23) Hackett, M.; Ibers, J . A.; Whitesides, G. M. J . Am. Chem. Soc.
1988, 110, 1436-1448.
(24) Davies, J . A.; Staples, R. J . Polyhedron 1991, 10, 909-917.
(25) Irisli, S.; Sarikahya, Y. Synth. React. Inorg. Met.-Org. Chem.
1995, 25, 965-975.
(26) Fischer, R. A.; Kaesz, H. D.; Khan, S. I.; Muller, H. J . Inorg.
Chem. 1990, 29, 1601-1602.
73%). 1H NMR (CD2Cl2): δ -0.658 (dd, J PH ) 5, 15 Hz, J PtH
58 Hz, 1 H, SH), 0.352 (dd, J PH ) 5, 7 Hz, J PtH ) 66 Hz, 3 H,
)
(27) Ladipo, F. T.; Anderson, G. K. Organometallics 1994, 13, 303-
306.

Insertion into M-H and M-C Bonds of Pt Compounds
Organometallics, Vol. 18, No. 2, 1999 233
1
Me), 1.1-2.4 (m, 44 H, Cy), 3.06 (t, J PH ) 9 Hz, 2 H, CH2). H
NMR (THF-d8): δ -0.910 (dd, J PH ) 6, 22 Hz, J PtH ) 61 Hz,
1 H, SH), 0.355 (dd, J PH ) 5, 7 Hz, J PtH ) 67 Hz, 3 H, Me),
1.2-2.4 (m, 44 H, Cy), 3.19 (t, J PH ) 9 Hz, 2 H, CH2). 31P NMR
(CD2Cl2): δ -27.95 (d, J PP ) 42 Hz, J PtH ) 1374 Hz), -28.98
(d, J PP ) 42 Hz, J PtH ) 2803 Hz). 31P NMR (THF-d8): δ -26.76
(d, J PP ) 43 Hz, J PtH ) 1376 Hz), -28.36 (d, J PP ) 43 Hz, J PtH
) 2727 Hz). Anal. Calcd for C26H50P2PtS‚1/3CH2Cl2: C, 46.51;
H, 7.51. Found: C, 46.52; H, 7.73.
Rea ction of P t(d cp e)(Me)(SH) w ith Br 2. A 14 mg (0.021
mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to a standard
NMR tube and dissolved in 0.5 mL of CD2Cl2. A 1.8 µL aliquot
of Br2 (0.035 mmol) was added to the tube, and this solution
was mixed for 1 h, at which time the solution had turned
orange. NMR analysis indicated that most of the starting
material had converted to Pt(dcpe)Br2, with some of the PtIV
complex remaining. The presence of the PtIV species, presum-
ably cis-Pt(dcpe)(Me)(SH)Br2, is based on the 31P NMR spec-
trum (CD2Cl2), which showed a resonance at δ 41.06 (s, J PtP
2028 Hz).
)
Rea ction of P t(d cp e)(Me)(SH) a n d p-Xylen e-d 10. A 12
mg (0.018 mmol) amount of Pt(dcpe)(Me)(SH) was added to
an NMR tube and dissolved in about 1 mL of dry, oxygen-free
p-xylene-d10, followed by immersion in a 130 °C oil bath. After
24 h of heating, the starting material had quantitatively
converted into a new product with the loss of CH4, as
determined by NMR spectroscopy. Recrystallization of the
product from a p-xylene-d10 solution layered with hexanes
resulted in a yellow powder assigned as [Pt(dcpe)(µ-S)]2. 1H
NMR (p-xylene-d10): δ 1.3-3.0 (m). 31P NMR (p-xylene-d10):
δ 65.01 (s, J PtH ) 2648 Hz). Anal. Calcd for C52H96P4Pt2S2: C,
48.06; H, 7.45. Found: C, 47.71; H, 7.79.
Rea ction of P t(d cp e)(Me)(SH) w ith MeI. A 21 mg (0.032
mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to a NMR
tube and dissolved in about 1 mL of dry oxygen-free CD2Cl2.
The NMR tube was unsealed, and 0.002 mL of MeI (0.032
mmol) was added. After 20 h at ambient temperature, the
starting material had been quantitatively converted to Pt-
(dcpe)I2, as determined by NMR spectroscopy.
cis-Disu lfh yd r yl[bis(d icycloh exylp h osp h in o)eth a n e]-
p la tin u m (II) (6). A solution of 40 mg (0.058 mmol) of Pt(dcpe)-
Cl2 in 6 mL of THF was treated with 14 mg (0.25 mmol) of
NaSH. The solution was stirred at ambient temperature for
15 h, resulting in a cloudy yellow solution. The solution was
evaporated and the residue extracted with H2O and CH2Cl2.
The organic fractions were combined, dried over MgSO4, and
evaporated to dryness on a rotary evaporator. Recrystallization
from a CH2Cl2 solution layered with hexanes yielded yellow
cis-Ch lor om eth yl[bis(d icycloh exylp h osp h in o)eth a n e]-
p a lla d iu m (II). A solution of 90 mg (0.34 mmol) of Pd(COD)-
(Me)Cl in 15 mL of C6H6 was treated with 14 mg (0.34 mmol)
of Cy2PC2H4PCy2. The tan solution was stirred for 2 h,
resulting in a clear solution that was evaporated in vacuo to
produce an ivory-colored powder of Pd(dcpe)(Me)Cl (173 mg,
88%). The product was recrystallized from a CH2Cl2 solution
layered with hexanes. 1H NMR (CDCl3): δ 0.483 (dd, J PH ) 8,
2 Hz, 3 H, Me), 1.1-2.1 (m, 48 H, Cy2PC2H4PCy2). 31P NMR
(CDCl3): δ 60.66 (d, J PP ) 18 Hz), 75.99 (d, J PP ) 19 Hz). Anal.
Calcd for C27H51ClP2Pd‚2CH2Cl2: C, 46.48; H, 7.40. Found: C,
46.99; H, 7.22.
1
crystals of Pt(dcpe)(SH)2 (6; 39 mg, 98%). H NMR (C6D6): δ
0.282 (dd, J PH ) 6, 9 Hz, J PtH ) 59 Hz, 2 H, SH), 1.0-2.4 (m,
48 H, Cy2PC2H4PCy2). 31P NMR (C6D6): δ 64.08 (s, J PtP ) 2799
Hz). Anal. Calcd for C26H50P2PtS2: C, 52.47; H, 8.47. Found:
C, 52.22; H, 8.56.
Rea ction of P t(d cp e)(Me)(SH) w ith H2S. A 8 mg (0.012
mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to an NMR
tube and dissolved in about 0.5 mL of dry oxygen-free C6D6.
The NMR tube was briefly opened to 1 atm of H2S gas. After
20 h at ambient temperature, the sample was evaporated to
remove excess H2S and then redissolved in C6D6. The starting
material had been quantitatively converted to Pt(dcpe)(SH)2,
as determined by NMR spectroscopy.
P h otolysis of P t(Cy2P C2H4P Cy2)(Me)(SH). A 13 mg
(0.020 mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to an
NMR tube and dissolved in about 1 mL of dry, oxygen-free
THF-d8. Photolysis of the sample using a Xe/Hg lamp (λmax
>300 nm) for 24 h resulted in decomposition of the starting
material and generation of a small quantity (∼10%) of CH4,
as determined by NMR spectroscopy.
cis-Su lfh yd r ylm e t h yl[b is(d icycloh e xylp h osp h in o)-
eth a n e]p a lla d iu m (II) (5). A solution of 65 mg (0.11 mmol)
of Pd(dcpe)(Me)Cl in 10 mL of THF was treated with 28 mg
(0.50 mmol) of NaSH. The solution was stirred at ambient
temperature for 2 h, resulting in an orange solution. The
solution was evaporated and extracted with H2O and CH2Cl2.
All organic layers were combined, dried with MgSO4, and
evaporated to dryness on a rotary evaporator to yield an
orangish tan solid. Recrystallization from a CH2Cl2 solution
layered with hexanes yielded amber crystals of Pd(dcpe)(Me)-
1
(SH) (5; 48 mg, 74%). H NMR (C6D6): δ 0.248 (dd, J PH ) 5,
16 Hz, 3 H, Me), 0.225 (dd, J PH ) 6, 8 Hz, 3 H, Me), 1.1-2.1
(m, 48 H, Cy2PC2H4PCy2). 31P NMR (C6D6): δ 68.28 (d, J PP
20 Hz), 63.26 (d, J PP ) 17 Hz). Anal. Calcd for C27H52P2PdS‚
CH2Cl2: C, 50.79; H, 8.22. Found: C, 50.39; H, 7.96.
)
cis-(Me t h ylsu lfin a t o)m e t h yl[b is(d icycloh e xylp h os-
p h in o)eth a n e]p la tin u m (II) (7). A 24 mg (0.037 mmol)
amount of Pt(dcpe)(Me)2 was added to an NMR tube and
dissolved in about 1 mL of dry, oxygen-free THF-d8. The NMR
tube was briefly opened to 1 atm of SO2 gas. After 20 h at
room temperature, the starting material had been quantita-
tively converted to Pt(dcpe)(SO2Me)Me (7), as determined by
NMR spectroscopy. The product was isolated by removal of
the solvent under vacuum and recrystallization from a CH2-
Cl2 solution layered with hexanes. 1H NMR (THF-d8): δ 0.557
(dd, J PH ) 6, 4 Hz, J PtH ) 61 Hz, 3 H, Me), 1.1-2.6 (m, 52 H,
Rea ction of P t(d cp e)(Me)(SH) w ith 12 M HCl. A 22 mg
(0.033 mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to a
standard NMR tube and dissolved in 1 mL of C6D6. Two drops
of 12 M HCl(aq) was added to the tube and mixed for 1 h,
resulting in the formation of a white precipitate. Filtration of
the white precipitate followed by NMR spectroscopic analysis
indicated that the starting material had been converted to Pt-
(dcpe)Cl2.
Rea ction of P t(d cp e)(Me)(SH) w ith 6 M HCl. A 15 mg
(0.023 mmol) amount of Pt(dcpe)(Me)(SH) (1) was added to a
standard NMR tube and dissolved in 0.5 mL of C6D6. To the
sample was added 0.008 mL (0.048 mmol) 6 M HCl(aq), and
this solution was mixed for 15 h. NMR spectroscopic analysis
of the resulting yellow solution indicated the formation of Pt-
(dcpe)(Me)Cl and the presence of H2S.
Cy2PCH2PCy2 and Me). 31P NMR (THF-d8): δ 53.36 (s, J PtP
)
2499 Hz), 71.73 (s, J PtP ) 1919 Hz). Anal. Calcd for C28H54O2P2-
PtS‚2CH2Cl2: C, 40.87; H, 6.63. Found: C, 40.97; H, 7.03.
Rea ction of P t(d cp e)(Me)Cl a n d SO2. A 20 mg (0.030
mmol) amount of Pt(dcpe)(Me)Cl was added to a NMR tube
and dissolved in about 1 mL of dry, oxygen-free THF-d8. The
NMR tube was briefly opened to 1 atm of SO2 gas. After 24 h
at 65 °C, the starting material had completely reacted to form
a 1:1 ratio of Pt(dcpe)(SO2Me)Me (7) and Pt(dcpe)Cl2, as
determined by NMR spectroscopy.
Rea ction of P t(d cp e)(Me)(SH) w ith I2. A 22 mg (0.033
mmol) amount of Pt(dcpe)(Me)(SH) (1) and a 10 mg (0.040
mmol) amount of I2 were placed in a standard NMR tube and
dissolved in about 1 mL of CD2Cl2, followed by sonication to
ensure all the I2 dissolved. After 1 h at ambient temperature,
the starting material had been quantitatively converted to Pt-
(dcpe)I2, as determined by NMR spectroscopy.
Rea ction of P t(d cp e)(SO2Me)Me a n d 12 M HCl. A 15
mg (0.020 mmol) amount of Pt(dcpe)(SO2Me)Me (7) was added
to a standard NMR tube and dissolved in 1 mL of THF-d8.

234 Organometallics, Vol. 18, No. 2, 1999
Morton et al.
Two drops of 12 M HCl(aq) was added to the tube. After 4 h
at ambient temperature, a clear solution and a white precipi-
tate formed. NMR spectroscopic analysis showed that the
starting material had quantitatively converted to Pt(dcpe)Cl2,
MeSO2H, and CH4.
cis-Dip h e n yl[b is(d icycloh e xylp h osp h in o)e t h a n e ]-
p la tin u m (II). A solution of 80 mg (0.116 mmol) of Pt(dcpe)-
Cl2 in 6 mL of THF was treated with 20 mg (0.238 mmol) of
PhLi and stirred at ambient temperature for 2 h. The resulting
milky solution was quenched with a saturated NH4Br solution
and evaporated, and the residue was extracted with diethyl
ether. The combined organic layers were dried with MgSO4
and evaporated to dryness on a rotary evaporator to yield a
white solid. Recrystallization from a CH2Cl2 solution layered
with hexanes resulted in white crystals of Pt(dcpe)Ph2 (58 mg,
64%). 1H NMR (C6D6): δ 0.8-2.0 (m, 48 H, Cy2PC2H4PCy2),
employing full-matrix least squares on F2 (Siemens, SHELX-
TL,30 version 5.04). All of the non-H atoms of the molecular
species were refined anisotropically for all the data sets, except
for C(9) in 7, which tended toward NPD. The hydrogen atoms
were included in idealized positions for all the structures. For
a Z value of 4, 3 contained one molecule and an acetone
solvent, which was disordered over two positions, in the
asymmetric unit. Hydrogen atoms were not included for the
disordered solvent atoms. For a Z value of 16, 2 contained two
molecules and two THF solvents in the asymmetric unit. For
a Z value of 4, 7 contained one molecule and a CH2Cl2 solvent
in the asymmetric unit. The final residuals and goodness-of-
fit values,31 as well as further details of the data collection
and refinement, are provided in Table 1.
Ack n ow led gm en t is made to the U.S. Department
of Energy, Grant No. FG0286ER13569, for their partial
support of this work. M.S.M. also thanks Elf Atochem,
NA, for financial support.
6.92 (t, J PH ) 7 Hz, 2 H, Ph), 7.21 (m, 4 H, Ph), 7.79 (t, J PH
)
7 Hz, J PtH ) 58 Hz, 4 H, Ph). 31P NMR (C6D6): δ 55.24 (s, J PtP
) 1725 Hz). Anal. Calcd for C38H58P2Pt‚CH2Cl2: C, 54.67; H,
7.06. Found: C, 54.52; H, 7.60.
X-r a y Exp er im en ta l Deta ils for 2, 3, a n d 7. The X-ray
intensity data were collected on a standard Siemens SMART
CCD Area Detector System equipped with a normal-focus
molybdenum-target X-ray tube operated at 2.0 kW (50 kV, 40
mA). A total of 1321 frames of data (1.3 hemispheres) were
collected using a narrow frame method with scan widths of
0.3° in ω and exposure times of either 10 s/frame using a
detector-to-crystal distance of 5.09 cm (maximum 2θ angle of
56.6°). The total data collection time was approximately 6 h.
Frames were integrated to 0.90 Å for 2 and to 0.75 Å for 3
and 7 with the Siemens SAINT program. Laue symmetry
revealed monoclinic crystal systems for 2 and 3 and an
orthorhombic crystal system for 7. The final unit cell param-
eters (at -80 °C) were determined from the least-squares
refinement of three-dimensional centroids of >5000 reflections
for all the crystals.28 Data were corrected for absorption with
the SADABS29 program.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic data, atom coordinates, thermal parameters, and
bond distances and angles for 2, 3, and 7 (23 pages). Ordering
information is given on any current masthead page.
OM980772S
(28) It has been noted that the integration program SAINT produces
cell constant errors that are unreasonably small, since systematic error
is not included. More reasonable errors might be estimated at 10×
the listed value. It should be noted that the SAINT program could not
improve the original cell produced by SMART for 11, and hence the
final unit cell is based upon only 168 reflections.
(29) The SADABS program is based on the method of Blessing;
see: Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(30) SHELXTL: Structure Analysis Program, version 5.04; Siemens
Industrial Automation Inc.: Madison, WI, 1995.
(31) GOF ) [∑[w(F2o - F2c)2]/(n - p)]1/2, where n and p denote the
number of data and parameters. R1 ) (∑|Fo| - |Fc|)/∑|Fo|, and wR2 )
[∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]]1/2, where w ) 1/[σ2(F2o) + (aP)2 + bP] and P
) [(Max;0,F2o) + 2Fc2]/3.
The space group assignments are provided in Table 1. The
structures were solved by using direct methods and refined