Preparation of Half-Sandwich Alkoxycarbene Complexes of Osmium(II)

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• 作者：Gabriele Albertin ; Stefano Antoniutti ; Jesu虂s Castro
• 刊名：Organometallics
• 出版年：2011
• 出版时间：March 28, 2011
• 年：2011
• 卷：30
• 期：6
• 页码：1558-1568
• 全文大小：1016K
• 年卷期：v.30,no.6(March 28, 2011)
• ISSN：1520-6041

文摘

Alkoxy-alkylcarbene complexes [OsCl{鈺怌(OR鈥?CH₂R鈥测€瞹(畏⁶-p-cymene)L]BPh₄ (1鈭?b>4) [R鈥?= Me, Et; R鈥测€?= Ph, p-tolyl, Bu^t; L = P(OMe)₃, P(OEt)₃, PPh(OEt)₂, PPh₂OEt] were prepared by allowing dichloro compounds OsCl₂(畏⁶-p-cymene)L to react with terminal alkyne R鈥测€睠鈮H in alcohol. Ethoxy-methylcarbene [OsCl{鈺怌(OEt)CH₃}(畏⁶-p-cymene)L]BPh₄ (5) was also prepared from reaction with trimethylsilyl acetylene. A reaction path for the formation of compounds 1鈭?b>5, involving the nucleophilic attack of alcohol on intermediate vinylidene complexes, is discussed. Acetylide derivatives OsCl(C鈮Ar)(畏⁶-p-cymene)L (6, 7) [Ar = Ph, p-tolyl; L = P(OMe)₃, P(OEt)₃, PPh(OEt)₂] were prepared by reacting dichloro compounds OsCl₂(畏⁶-p-cymene)L with lithium acetylide (Li⁺[ArC鈮]^{鈭?/sup>) in thf. Protonation reaction with Br酶nsted acids of 6 and 7 led to vinylidene cations [OsCl{鈺怌鈺怌(H)Ar}(畏6-p-cymene)L]+. Complexes OsCl₂(畏6-p-cymene)L also reacted with both PhC鈮H and (CH₃)₃SiC鈮H in the presence of H₂O to give alkyl-carbonyl derivatives [Os(畏1-CH₂Ph)(CO)(畏6-p-cymene)L]BPh₄ (8) and [Os(畏1-CH₃)(CO)(畏6-p-cymene)L]BPh₄ (9). The complexes were characterized spectroscopically (IR and 1H, 13C, 31P NMR) and by X-ray crystal structure determinations of [OsCl{鈺怌(OEt)CH₂Ph}(畏6-p-cymene){PPh(OEt)₂}]BPh₄ (1c), [OsCl{鈺怌(OEt)CH₂Ph}(畏6-p-cymene)(PPh₂OEt)]BPh₄ (1d), and [Os(畏1-CH₂Ph)(CO)(畏6-p-cymene){PPh(OEt)₂}]BPh₄ (8c).}