Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes

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• 作者：Andrew J. Roering ; Sarah E. Leshinski ; Stephanie M. Chan ; Tamila Shalumova ; Samantha N. MacMillan ; Joseph M. Tanski ; Rory Waterman
• 刊名：Organometallics
• 出版年：2010
• 出版时间：June 14, 2010
• 年：2010
• 卷：29
• 期：11
• 页码：2557-2565
• 全文大小：912K
• 年卷期：v.29,no.11(June 14, 2010)
• ISSN：1520-6041

文摘

Triamidoamine-supported zirconium phosphido complexes, (N₃N)ZrPRR′ (N₃N = N(CH₂CH₂NSiMe₃)₃³⁻; R = alkyl, aryl; R′ = R, H), have been shown to catalyze the hydrophosphination of terminal alkynes as well as that of symmetric aryl and alkyl carbodiimides. A mechanism based on insertion of the substrate into the Zr−P bond is proposed on the basis of competition experiments and model examples of stoichiometric insertion reactions of polar, small-molecule substrates possessing C═O, C═N, C≡N, and C═S functionalities into the Zr−P bond. Molecular structures of the insertion products (N₃N)ZrN═C(PHCy)Ph (4), (N₃N)ZrN═C(PPh₂)Ph (5), and (N₃N)ZrPhNC(O)PPh₂ (11), as well as (N₃N)Zr[η²(N,N)-(ⁱPrN)₂C(PPh₂)] (9), a key intermediate in the catalytic hydrophosphination of carbodiimides, have been determined.