Ruthenium Silyl Complexes
Organometallics, Vol. 21, No. 22, 2002 4783
over [Cp2TiCl]2ZnCl2.34 CD2Cl2 was stored over CaH2. C6D6 was
dried using NaK and stored over [Cp2TiCl]2ZnCl2.34 All solvents
were transferred under vacuum.
rated to dryness to afford 8 as a yellow solid (75 mg, 80%).
The reaction of 1, 2, or 3 with LiAlH4 in Et2O was used to
prepare 7. Typical yields of 7 and 8 were between 75 and 85%.
Anal. Calcd for C21H30P2RuSi (7): C, 53.26; H, 6.39. Found:
C, 52.84; H, 6.02. Anal. Calcd for C22H32P2RuSi (8): C, 54.19;
H, 6.61. Found: C, 53.56; H, 6.13.
Cp (P P h Me2)2Ru SiMe3 (9). AlMe3 (0.27 mL, 0.554 mmol)
was added by syringe to a cold suspension of 1 (100 mg, 0.173
mmol) in toluene (25 mL) under an argon atmosphere. Upon
addition of the AlMe3, complex 1 dissolved to give a bright
yellow solution, which was allowed to stir at room temperature
for 1 h. The reaction volatiles were removed under vacuum to
give a yellow paste. This paste was extracted with hexanes
(10 × 2 mL) and filtered through Celite. The yellow extracts
were evaporated to dryness to afford a yellow residue. This
residue was extracted again with hexanes and filtered through
Celite. The final yellow extract solution was evaporated to
dryness to afford 9 as a yellow solid (66.7 mg, 76%). Anal. Calcd
for C24H36P2RuSi (9): C, 55.90; H, 7.04. Found: C, 55.32; H,
6.52.
Cp (P P h Me2)2Ru SiX3 [SiX3 ) SiCl3 (1), SiHCl2 (2), SiH-
MeCl (4)]. These ruthenium silyl complexes were prepared
by the reaction of Cp(PPhMe2)2RuH with X3SiCl in CH2Cl2 in
the absence or presence of excess DBU. With ou t DBU. In a
typical reaction, CH2Cl2 (15 mL) was added by vacuum
transfer to a flask charged with Cp(PPhMe2)2RuH (50 mg,
0.113 mmol). Using calibrated gas-bulb techniques, SiCl4 (0.75
equiv) was transferred to the frozen Cp(PPhMe2)2RuH/
CH2Cl2 solution. The reaction mixture was allowed to slowly
warm to room temperature and stirred for ∼15 min. The
solution volume was reduced to ∼1/4 and then doubled with
hexanes to precipitate [Cp(PPhMe2)2RuH2]Cl. [Cp(PPhMe2)2-
RuH2]Cl was isolated by filtration. The yellow filtrate solu-
tion was evaporated to dryness to afford a mixture of 1 and
Cp(PPhMe2)2RuCl. With DBU. In a typical reaction, a flask
was charged with Cp(PPhMe2)2RuH (50 mg, 0.113 mmol), DBU
(25.3 µL, 0.169 mmol), and CH2Cl2 (15 mL) in the glovebox.
Using calibrated gas-bulb techniques, excess SiCl4 (1.5 equiv)
was transferred to the frozen Cp(PPhMe2)2RuH/DBU/CH2Cl2
solution. The frozen yellow mixture was warmed to room
temperature and allowed to stir for 1.5 h. The volatiles were
removed under vacuum to give a yellow-orange paste. This
paste was extracted with diethyl ether and filtered through
Celite. The extracts were reduced to 1/2 volume and tripled
with hexanes. The mixture was then reduced to 1/4 volume.
The precipitate was isolated by filtration and dried under
vacuum to afford 1 as a pale yellow solid (57.5 mg, 88.2%).
Typical yields for 1, 2, and 4 were in the range of 80-90%.
Cp (P P h 2Me)2Ru SiHCl2 (5). This ruthenium silyl complex
was prepared by the direct reaction of Cp(PPh2Me)2RuH with
HSiCl3 in CH2Cl2. Typically, CH2Cl2 (15 mL) was added by
vacuum transfer to a 25 mL O-ring, Kjeldahl flask charged
with Cp(PPh2Me)2RuH (200 mg, 0.352 mmol). HSiCl3 (1.5
equiv) was transferred using calibrated gas-bulb techniques
to the liquid nitrogen cooled flask. The reaction mixture was
slowly allowed to warm to room temperature and stirred for 1
h. The reaction volatiles were removed under vacuum to give
a dark yellow-orange residue. The residue was taken up in
CH2Cl2 (∼0.5 mL) and pipetted into a 10 × 75 mm test tube,
hexanes (∼1.5 mL) were carefully layered on top of the
CH2Cl2 solution, and the entire setup was cooled to -30 °C in
the glovebox. Complex 5 was obtained as a crystalline yellow
solid (10 mg, 8.5%). Anal. Calcd for C31H32P2Cl2RuSi (5): C,
55.86; H, 4.84. Found: C, 54.84; H, 4.03. [Cp(PPh2Me)2RuH2]-
Cl: 1H NMR (CD2Cl2) δ 7.45(m, 20H, PPh), 5.11 (s, 5H, Cp),
Anal. Calcd for
C
21H27Cl3P2RuSi (1): C, 43.72; H, 4.72.
Found: C, 43.28; H, 4.66. Anal. Calcd for C21H28Cl2P2RuSi
(2): C, 46.50; H, 5.20. Found: C, 46.39; H, 4.97. Anal. Calcd
for C22H31ClP2RuSi (4): C, 50.62; H, 5.99. Found C, 49.65; H,
5.43. [Cp(PhMe2)2RuH2]Cl: 1H NMR (CD2Cl2) δ 7.44 (m, 10H,
PPh), 5.21 (s, 5H, Cp), 1.78 (fd, N ) 9.6 Hz, 12H, PMe2), -9.13
2
(t, J PH ) 27.7 Hz, 2H, RuH2); 31P{1H} NMR (CD2Cl2) δ 25.12
2
1.85 (fd, N ) 9.2 Hz, 6H, PMe), -8.43 (t, J PH ) 25.4 Hz, 2H,
RuH2); 31P{1H} NMR (CD2Cl2) δ 41.10 (s).
(s).
Cp (P R3)2Ru SiH2Cl [P R3 ) P P h Me2 (3), P P h 2Me (6)].
These ruthenium silyl complexes were prepared by the reac-
tion of Cp(PR3)2RuH with SiH2Cl2 in CH2Cl2. However, this
reaction was complicated by formation of Cp(PR3)2RuCl, and
due to the similar solubilities of 3 or 6 and the corresponding
Cp(PR3)2RuCl, analytically pure samples of 3 or 6 were not
obtained. In a typical reaction, CH2Cl2 (15 mL) was added by
vacuum transfer to a flask charged with Cp(PPh2Me)2RuH
(50 mg, 0.088 mmol). Using calibrated gas-bulb techniques,
SiH2Cl2 (0.75 equiv) was transferred to the frozen
Cp(PPh2Me)2RuH/CH2Cl2 solution. The reaction mixture
was allowed to slowly warm and stirred at room tempera-
ture for ∼15 min. The solution volume was reduced to ∼1/4
and then doubled with hexanes. The resulting solid was
isolated by filtration to give 40 mg of a light orange solid,
which was determined (by 1H NMR) to be a mixture of 6,
Cp(PPh2Me)2RuCl, and [Cp(PPh2Me)2RuH2]Cl. Similarly, 3
was obtained contaminated with Cp(PPhMe2)2RuCl, even with
the addition of DBU as described above.
Cp (P P h Me2)2Ru SiH2X [SiH2X ) SiH3 (7), SiH2Me (8)].
These ruthenium hydrosilyl derivatives were prepared by the
reaction of LiAlH4 with the respective chlorosilyl complex. In
a typical reaction, a 25 mL Kjeldahl flask was charged with 4
(100 mg, 0.192 mmol) and LiAlH4 (25 mg, 0.659 mmol). Et2O
(15 mL) was added to the mixture by vacuum transfer. The
yellow solution was allowed to stir for 1.5 h at room temper-
ature. The solvent was removed under vacuum to give a light
gray residue. The residue was extracted with hexanes (15 mL)
and filtered through Celite. The yellow extracts were evapo-
Cp (P P h 2Me)2Ru Me. This ruthenium alkyl was prepared
by an adaptation of the literature method.35 A 25 mL, sidearm
Schlenk flask, equipped with a condenser and magnetic stir-
bar, was charged with Cp(PPh2Me)2RuCl (100 mg, 0.166
mmol). THF (∼15 mL) was transferred to the flask via vacuum.
Under a heavy flow of argon, MeMgCl (2 equiv) was added by
syringe to the cool, stirring reaction mixture. The orange
reaction mixture was heated to reflux for 16 h. The reaction
volatiles were removed under vacuum to give a brown-yellow
residue. The residue was extracted with hexanes (∼25 × 1.5
mL) and filtered through Celite. The bright yellow solution
was evaporated to dryness to afford Cp(PPh2Me)2RuMe as a
bright yellow solid (85 mg, 88%). 1H NMR (CD2Cl2): δ 7.23
(m, 20H, PPh2), 4.35 (s, 5H, Cp), 1.32 (fd, N ) 7.85 Hz, 6H,
3
PMe), 0.13 (t, J PH ) 5.9 Hz, 3H, RuMe). 31P{1H} NMR
(CD2Cl2): δ 42.53 (s). 13C{1H} (CD2Cl2): δ 145.36, (vt, N )
38.44, Hz, ipso-PPh), 141.25 (vt, N ) 39.37 Hz, ipso-P′Ph),
133.29 (vt, N ) 10.98 Hz, ortho-PPh), 131.09 (vt, N ) 10.07
Hz, ortho-P′Ph), 128.82 (s, para-PPh), 128.02 (s, para-P′Ph),
127.80 (vt, N ) 9.15 Hz, meta-PPh) 127.60 (vt, N ) 8.24, meta-
2
PPh), 82.85 (t, J PC ) 2.29 Hz, Cp), 15.72 (vt, N ) 25.64 Hz,
2
PMe), -26.78 (t, J PC ) 14.19 Hz, RuMe).
Cp (P P h 2Me)2Ru SiX3 [SiX3 ) SiCl3 (10), SiMeCl2 (11)].
In a typical reaction, a 50 mL round-bottom reaction vessel,
equipped with a Teflon plug and stir bar, was charged with
Cp(PPh2Me)2RuMe (50 mg, 0.086 mmol) and HSiCl3 (∼25 mL).
While frozen with liquid nitrogen, the headspace above this
mixture was evacuated. The reaction mixture was allowed to
(35) Bruce, M. I.; Gardner, R. C. F.; Howard, J . A. K.; Stone, F. G.
A.; Welling, M.; Woodward, P. J . Chem. Soc., Dalton Trans. 1977, 621-
629.
(34) Sekutowski, D. G.; Stucky, G. D. Inorg. Chem. 1975, 14, 2192-
2199.
Freeman, Samuel T.N.
