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.