Exploring the Utility of Neutral Rhodium and Iridium 2-P,O and 2-P(S),O Complexes as Catalysts for Alkene Hydrogenation and Hydrosilylation

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• 作者：Kevin D. Hesp ; Dominik Wechsler ; Judy Cipot ; Anne Myers ; Robert McDonald ; Michael J. Ferguson ; Gabriele Schatte ; Mark Stradiotto
• 刊名：Organometallics
• 出版年：2007
• 出版时间：October 22, 2007
• 年：2007
• 卷：26
• 期：22
• 页码：5430 - 5437
• 全文大小：180K
• 年卷期：v.26,no.22(October 22, 2007)
• ISSN：1520-6041

文摘

Heating of [(COD)M(²-3-PⁱPr₂-2-NMe₂-indene)]⁺X^- (M = Rh or Ir; X = BF₄, PF₆; COD = ⁴-1,5-cyclooctadiene) in a mixture of water and THF (48 h, 60 C) afforded the neutral (COD)M(²-P,O)complexes (M = Rh, 5a, 80%; M = Ir, 5b, 74%). Similarly, thermolysis of [(COD)M(²-3-P(S)ⁱPr₂-2-NMe₂-indene)]⁺BF₄^- (M = Rh or Ir) in a mixture of water and CH₂Cl₂ (14 h, 60 C) produced theneutral (COD)M(²-P(S),O) complexes (M = Rh, 13a, 91%; M = Ir, 13b, 90%). Subsequent preparationof 1-PⁱPr₂-2-indanone (8, 91%) enabled the non-hydrolytic synthesis of 5b in 70% isolated yield viatreatment with 0.5[(COD)IrCl]₂ in the presence of NEt₃. Lithiation of (o-PⁱPr₂)phenol followed byquenching with 0.5[(COD)IrCl]₂ afforded the neutral (COD)Ir(²-P,O) complex 10 (91%). Single-crystalX-ray diffraction data are provided for 5b, 10, 13a, and 13b. Whereas 5a, 13a, and 13b performedpoorly as catalysts for the hydrogenation of alkenes, the known complex (COD)Ir(OPh)(PCy₃) 2 as wellas 5b and 10 proved to be excellent catalysts for hydrogenation of mono-, di-, and trisubstituted alkenesubstrates under mild conditions (22 C, ~1 atm H₂). Complexes 13a,b were also shown to be competentcatalysts for addition of triethylsilane to styrene.