Activation of Water and of Dioxygen by a Bis(diphenylphosphinopropyl)silyl (biPSi) Complex of Ruthenium(II): Formation of Bis(diphenylphosphinopropyl)siloxo Cage Complexes. Concomitant Oxygen Atom Ins

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• 作者：Stephen R. Stobart ; Xiaobing (Joe) Zhou ; Raymundo Cea-Olivares ; and Alfredo Toscano
• 刊名：Organometallics
• 出版年：2001
• 出版时间：November 12, 2001
• 年：2001
• 卷：20
• 期：23
• 页码：4766 - 4768
• 全文大小：63K
• 年卷期：v.20,no.23(November 12, 2001)
• ISSN：1520-6041

文摘

The coordinatively saturated hydrido complexRuH(biPSi)(CO)₂ (1), biPSi = -Si(Me)(CH₂CH₂CH₂PPh₂)₂, reacts slowly with either water/piperidine ordioxygen to afford the novel "anchored" siloxo complexesRuH[OSiMe(CH₂CH₂CH₂PPh₂)₂](CO)L (3, L = CO) andRuH[OSi(OMe)(CH₂CH₂CH₂PPh₂)₂](CO)L (6, L = CO),respectively, which undergo carbonyl displacement toyield analogues in which L = P(OMe)₃ that are crystalline (5 or 7, respectively) and for which anti stereochemistry (i.e., H at Ru vs Me or OMe at Si) has beenidentified by using X-ray crystallography (i.e., products5-a, 7-a respectively). Complex 1 catalyzes autoxidationof cyclohexene (mainly to cyclohexenone, cyclohexenol:TTO 300, 4 h).