1802 Organometallics, Vol. 15, No. 7, 1996
Maddock et al.
3,5
1,3
Ru (CHdCHSiMe3)Cl(CO)2(P P h 3)2 (3a ). Ru(CHdCHSi-
Me3)Cl(CO)(PPh3)2 (0.130 g, 0.165 mmol) was dissolved in
dichloromethane (5 mL), and CO was bubbled through the
solution until it decolorized. The solvent volume was reduced
under reduced pressure and ethanol was added to precipitate
the white product. Recrystallization from dichloromethane/
ethanol gave pure 3a (0.082 g, 61%), mp 163-164 °C. Anal.
Calcd for C43H41ClO2P2RuSi: C, 63.27; H, 5.06. Found: C,
63.10; H, 4.87. 1H NMR (CDCl3; δ): 8.00 (dt, 1H, CHdCH,
meta,
J
) 10.6 Hz); 134.2 (t′, PPh3 ipso,
J
) 43.4 Hz);
CP
CP
129.5 (s, CNC6H4CH3); 129.3 (s, PPh3 para); 127.6 (t′, PPh3
2,4
ortho,
J
) 9.6 Hz); 125.5 (s, CNC6H4CH3); 21.3 (s,
CP
CNC6H4CH3); -1.4 (s, Si(CH3)).
Ru (CHdCHSiMe3)(η2-O2CCH3)(CO)(P P h 3)2 (5a ). Ru-
(CHdCHSiMe3)Cl(CO)(PPh3)2 (0.100 g, 0.127 mmol) was dis-
solved in dichloromethane (5 mL). A solution of sodium
acetate (0.050 g, 0.61 mmol) in water (1 mL) and ethanol (10
mL) was added, and the red solution turned colorless. On
reduction of the solvent volume the white product precipitated.
Recrystallization from dichloromethane/ethanol gave pure 5a
(0.090 g, 87%), mp 188-192 °C. Anal. Calcd for C44H44O3P2-
RuSi: C, 65.09; H, 5.46. Found: C, 64.76; H, 5.30. 1H NMR
3
3J HH ) 19.8 Hz, J HP ) 4.0 Hz); 7.81-7.31 (m, 30H, PPh3);
3
4
5.73 (dt, 1H, CHdCH, J HH ) 19.9 Hz, J HP ) 1.6 Hz); -0.32
(s, 9H, Si(CH3)). 13C NMR (CDCl3; δ): 197.6 (t, CO, J CP
)
2
2
2
11.4 Hz); 193.6 (t, CO, J CP ) 8.1 Hz); 175.0 (t, CHdCH, J CP
3
3
3
) 13.7 Hz); 143.9 (t, CHdCH, J CP ) 3.7 Hz); 134.1 (t′, PPh3
(CDCl3; δ): 7.73 (dt, 1H, CHdCH, J HH ) 16.8 Hz, J HP ) 2.2
3,5
1,3
3
meta,
J
) 10.2 Hz); 133.2 (t′, PPh3 ipso,
129.9 (s, PPh3 para); 127.9 (t′, PPh3 ortho,
-1.6 (s, Si(CH3)).
J
J
CP
) 46.2 Hz);
) 9.6 Hz);
CP
CP
Hz); 7.55-7.38 (m, 30H, PPh3); 5.59 (dt, 1H, CHdCH, J HH
)
2,4
4
16.9 Hz, J HP ) 1.6 Hz); 0.61 (s, 3H, O2CCH3); -0.52 (s, 9H,
Si(CH3)). 13C NMR (CDCl3; δ): 206.2 (t, CO, J CP ) 15.7 Hz);
2
2
Ru (CHdCHSiEt3)Cl(CO)2(P P h 3)2 (3b). Ru(CHdCHSiEt3)-
Cl(CO)(PPh3)2 (0.105 g, 0.126 mmol) was dissolved in dichlo-
romethane (5 mL). CO was bubbled through the solution until
the orange color was discharged. The volume was reduced
under low pressure and ethanol added to effect crystallization
of the colorless product. Recrystallization from dichloromethane/
ethanol gave pure 3b (0.100 g, 92%), mp 161.5-163 °C. Anal.
Calcd for C46H47ClO2P2RuSi: C, 64.36; H, 5.52. Found: C,
64.23; H, 5.48. 1H NMR (CDCl3; δ): 8.23 (dt, 1H, CHdCH,
182.4 (s, O2CCH3); 170.4 (t, CHdCH, J CP ) 10.3 Hz); 134.3
(t′, PPh3 meta,
43.0 Hz); 129.7 (s, PPh3 para); 128.0 (t′, PPh3 ortho,
10.0 Hz); 22.1 (s, O2CCH3); -1.1 (s, Si(CH3)).
3,5
1,3
2,4
J
) 11.4 Hz); 131.5 (t′, PPh3 ipso,
J
J
)
)
CP
CP
CP
R u (CH dCH SiMe2OH )Cl(CO)(P P h 3)2 (6e). Ru(SiMe2-
OH)Cl(CO)(PPh3)2 (0.600 g, 0.785 mmol) was dissolved in
benzene (10 mL) in a Fisher-Porter bottle. The solution was
stirred under ethyne pressure (0.8 atm) for 5 h. The yellow
color of the starting material was gradually lost, and a white
precipitate appeared. The volume of benzene was reduced in
vacuo to approximately 5 mL, and ethanol (10 mL) was added
to precipitate the remaining product (0.550 g, 89%), mp 172-
174 °C. Anal. Calcd for C41H39ClO2P2RuSi: C, 62.31; H, 4.97.
Found: C, 62.45; H, 4.98. 1H NMR (CDCl3; δ): 7.70-7.67 (m,
10H, PPh3); 7.60 (dt, 1H, CHdCH, 3J HH ) 12.6 Hz, 3J HP ) 1.6
3
3J HH ) 20.1 Hz, J HP ) 4.0 Hz); 7.86-7.30 (m, 30H, PPh3);
5.86 (dt, 1H, CHdCH, 3J HH ) 20.1 Hz, 4J HP ) 1.6 Hz); 0.68 (t,
9H, Si(CH2CH3), 3J HH ) 7.9 Hz); 0.18 (q, 6H, Si(CH2CH3), 3J HH
) 7.8 Hz). 13C NMR (CDCl3; δ): 197.5 (t, CO, 2J CP ) 11.4 Hz);
2
2
193.4 (t, CO, J CP ) 8.4 Hz); 176.0 (t, CHdCH, J CP ) 13.6
3
Hz); 141.5 (t, CHdCH, J CP ) 3.7 Hz); 134.0 (t′, PPh3 meta,
3,5
1,3
2,4
J
) 10.6 Hz); 133.4 (t′, PPh3 ipso,
J
) 45.8 Hz); 130.0
) 9.8 Hz); 7.5 (s,
CP
CP
3
Hz); 7.51-7.33 (m, 20H, PPh3); 5.55 (oddt, 1H, CHdCH, J HH
) 12.6 Hz, J HP ) 2.3 Hz); 2.61 (d, 1H, SiOH, J HH ) 2.3 Hz);
-0.75 (s, 6H, Si(CH3)).
(s, PPh3 para); 128.0 (t′, PPh3 ortho,
J
CP
4
4
Si(CH2CH3)); 3.4 (s, Si(CH2CH3)). 29Si NMR (CH2Cl2/CDCl3
30%; δ): -6.1 (s).
Ru (CHdCHSiMe2OEt)Cl(CO)2(P P h 3)2 (3d). Ru(CHdCH-
SiMe2OEt)Cl(CO)(PPh3)2 (0.066 g, 0.081 mmol) was dissolved
in dichloromethane (5 mL). CO was bubbled through the
solution until the orange color was discharged. On reduction
of the volume and addition of ethanol the white product
precipitated. Recrystallization from dichloromethane/ethanol
gave pure 3d (0.061 g, 89%), mp 120-122 °C. Anal. Calcd
[Ru (CHdCHSiMe2OH)(CO)(NCMe)(P P h 3)2]ClO4 (7e).
Ru(CHdCHSiMe2OH)Cl(CO)(PPh3)2 (0.555 g, 0.702 mmol) was
suspended in dichloromethane (20 mL) and acetonitrile (0.180
g, 4.39 mmol). A solution of AgClO4 (0.153 g, 0.738 mmol) in
ethanol (10 mL) was added. The solution was stirred for 15
min during which time the initial suspension of starting
material was replaced by a precipitate of AgCl. After filtration
through Celite twice, the volume was reduced under reduced
pressure and ethanol added to effect crystallization of the
product (0.545 g, 91%), mp 154-155.5 °C. Anal. Calcd for
C43H42ClNO6P2RuSi: C, 57.68; H, 4.73; N, 1.56. Found: C,
57.44; H, 4.87; N, 1.67. 1H NMR (CDCl3; δ): 7.95 (dt, 1H,
for C44H43ClO3P2RuSi: C, 62.44; H, 5.12. Found: C, 62.26;
3
H, 5.03. 1H NMR (CDCl3; δ): 8.30 (dt, 1H, CHdCH, J HH
)
3
20.3 Hz, J HP ) 3.6 Hz); 7.84-7.30 (m, 30H, PPh3); 5.92 (dt,
3
4
1H, CHdCH, J HH ) 20.2 Hz, J HP ) 1.6 Hz); 3.12 (q, 2H,
3
3
OCH2CH3, J HH ) 7.0 Hz); 0.97 (t, 3H, OCH2CH3, J HH ) 7.0
Hz); -0.27 (s, 6H, Si(CH3)). 13C NMR (CDCl3; δ): 197.2 (t,
2
2
3
3
CO, J CP ) 11.3 Hz); 193.6 (t, CO, J CP ) 8.5 Hz); 180.9 (t,
CHdCH, J CP ) 13.6 Hz); 141.7 (t, CHdCH, J CP ) 3.7 Hz);
CHdCH, J HH ) 13.0 Hz, J HP ) 2.0 Hz); 7.56-7.44 (m, 30H,
2
3
3
4
PPh3); 5.87 (oddt, 1H, CHdCH, J HH ) 13.0 Hz, J HP ) 2.2
3,5
4
134.0 (t′, PPh3 meta,
J
) 10.0 Hz); 133.3 (t′, PPh3 ipso,
) 46.6 Hz); 130.1 (s, PPh3 para); 128.1 (t′, PPh3 ortho,
) 9.8 Hz); 57.7 (s, OCH2CH3); 18.6 (s, OCHCH3); -2.6
Hz); 4.99 (d, 1H, SiOH, J HH ) 2.4 Hz); 1.70 (s, 3H, NCCH3);
CP
1,3
-0.86 (s, 6H, Si(CH3)). 13C NMR (CDCl3; δ): 202.9 (t, CO,
J
J
CP
2,4
2J CP ) 17.5 Hz); 177.9 (t, CHdCH, J CP ) 9.9 Hz); 134.3 (t′,
2
CP
PPh3 meta, 3,5J CP ) 11.2 Hz); 130.7 (t′, PPh3 ipso, 1,3J CP ) 43.0
(s, Si(CH3)).
2,4
Hz); 130.5 (s, PPh3 para); 128.6 (t′, PPh3 ortho,
Hz); 2.8 (s, NCCH3); -0.4 (s, Si(CH3)).
J
) 9.4
Ru (CHdSHSiMe3)Cl(CO)CN-p-tolyl)(P P h 3)2 (4a ). Ru-
(CHdCHSiMe3)Cl(CO)(PPh3)2 (0.100 g, 0.127 mmol) was dis-
solved in dichloromethane (5 mL), and to this was added a
solution of p-tolyl isocyanide (0.016 g, 0.140 mmol) in dichlo-
romethane (3 mL). The orange solution decolorized, and on
addition of ethanol and reduction of the solvent volume a white
produce precipitated. Recrystallization from dichloromethane/
ethanol give pure 4a (0.061 g, 52%), mp 159-163 °C. Anal.
Calcd for C50H48ClNOP2RuSi: C, 66.32; H, 5.34; N, 1.55.
Found: C, 66.35; H, 5.24; N, 1.50. 1H NMR (CDCl3; δ): 8.30
CP
[R u (CH dCH SiMe2OH )(CO)2(P P h 3)2]ClO4 (8e). [Ru-
(CHdCHSiMe2OH)(CO)(NCMe)(PPh3)2]ClO4 (0.410 g, 0.458
mmol) was dissolved in dichloromethane (20 mL) in a Fisher-
Porter bottle. The solution was placed under CO pressure (2
atm) and stirred for 30 min. The solvent volume was reduced,
and ethanol was added to effect precipitation. Recrystalliza-
tion from dichloromethane/ethanol gave pure 8e (0.315 g, 78%),
mp 138-140 °C. Anal. Calcd for C42H39ClO7P2RuSi‚
0.25CH2Cl2: C, 56.16; H, 4.41. Found: C, 56.09; H, 4.67. 1H
3
3
(dt, 1H, CHdCH, J HH ) 20.1 Hz, J HP ) 3.4 Hz); 7.88-7.30
(m, 30H, PPh3); 6.98 (d, 2H, CNC6H4CH3, 3J HH ) 8.3 Hz); 6.40
3
3
3
(d, 2H, CNC6H4CH3, J HH ) 8.4 Hz); 5.69 (dt, 1H, CHdCH,
NMR (CDCl3; δ): 7.69 (dt, 1H, CHdCH, J HH ) 13.6 Hz, J HP
) 2.3 Hz); 7.51-7.40 (m, 30H, PPh3); 6.19 (d, 1H, CHdCH,
3J HH ) 13.6 Hz); 5.60 (s, 1H, SiOH); 0.84 (s, 6H, Si(CH3)).
3J HH ) 20.2 Hz, J HP ) 1.6 Hz); 2.31 (s, 3H, CNC6H4CH3);
4
-0.32 (s, 9H, Si(CH3)). 13C NMR (CDCl3; δ): 200.3 (t, CO,
2J CP ) 12.7 Hz); 178.7 (t, CHdCH, J CP ) 13.6 Hz); 142.2 (t,
2
CHdCH, 3J CP ) 3.8 Hz); 138.8 (s, CNC6H4CH3); 134.3 (t′, PPh3
[R u (CH dCH SiMe2OH )(CO)(CN-p -t olyl)(P P h 3)2]ClO4