TY - JOUR
T1 - Reactions of a hydrido(hydrosilylene)tungsten complex with oxiranes
AU - Hashimoto, Hisako
AU - Ochiai, Mitsuyoshi
AU - Tobita, Hiromi
N1 - Funding Information:
This work was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grants-in-Aid for Scientific Research Nos. 14204065, 14078202, and 14044010).
PY - 2007/1/1
Y1 - 2007/1/1
N2 - Reactivity of a hydrido(hydrosilylene)tungsten complex, Cp*(CO)2(H)W{double bond, long}Si(H)[C(SiMe3)3] (1), toward oxiranes was investigated. Treatment of 1 with racemic mono-substituted oxiranes with a substituent R (R = Ph, vinyl, tBu, or nBu) at room temperature produced dihydrido(vinyloxysilyl)tungsten complexes, (E)- and/or (Z)-Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CHR)[C(SiMe3)3]} [(E/Z)-2: R = Ph, (E)-3: R = vinyl, (E)-4: R = tBu, (E/Z)-5: R = nBu] in high yields via regioselective ring-opening of oxiranes. When the substituent R on oxirane was relatively large, (E)-isomers (2, 3, and 4) were obtained predominantly (87-97%), while the substituent was a relatively small nBu group, an approximately 1:1 mixture of (E)- and (Z)-isomers [(E/Z)-5] was obtained. Reaction of 1 with 2,2-dimethyloxirane afforded the corresponding complex, Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CMe2)[C(SiMe3)3]} (6), quantitatively. A reaction mechanism is also discussed.
AB - Reactivity of a hydrido(hydrosilylene)tungsten complex, Cp*(CO)2(H)W{double bond, long}Si(H)[C(SiMe3)3] (1), toward oxiranes was investigated. Treatment of 1 with racemic mono-substituted oxiranes with a substituent R (R = Ph, vinyl, tBu, or nBu) at room temperature produced dihydrido(vinyloxysilyl)tungsten complexes, (E)- and/or (Z)-Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CHR)[C(SiMe3)3]} [(E/Z)-2: R = Ph, (E)-3: R = vinyl, (E)-4: R = tBu, (E/Z)-5: R = nBu] in high yields via regioselective ring-opening of oxiranes. When the substituent R on oxirane was relatively large, (E)-isomers (2, 3, and 4) were obtained predominantly (87-97%), while the substituent was a relatively small nBu group, an approximately 1:1 mixture of (E)- and (Z)-isomers [(E/Z)-5] was obtained. Reaction of 1 with 2,2-dimethyloxirane afforded the corresponding complex, Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CMe2)[C(SiMe3)3]} (6), quantitatively. A reaction mechanism is also discussed.
KW - (E/Z)-isomers
KW - Hydrido complex
KW - Oxirane
KW - Ring-opening reaction
KW - Silyl complex
KW - Silylene complex
KW - Vinyl group
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U2 - 10.1016/j.jorganchem.2006.08.071
DO - 10.1016/j.jorganchem.2006.08.071
M3 - Article
AN - SCOPUS:33845632036
SN - 0022-328X
VL - 692
SP - 36
EP - 43
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-3
ER -