Group-Transfer Reactions of Nickel−Carbene and −Nitrene Complexes with Organoazides and Nitrous Oxide that Form New C═N, C═O, and N═N Bonds

详细信息    查看全文

• 作者：Nicole D. Harrold ; Rory Waterman ; Gregory L. Hillhouse ; Thomas R. Cundari
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：September 16, 2009
• 年：2009
• 卷：131
• 期：36
• 页码：12872-12873
• 全文大小：159K
• 年卷期：v.131,no.36(September 16, 2009)
• ISSN：1520-5126

文摘

1-Adamantyl- and mesitylazide react with (dtbpe)Ni═CPh₂ (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) at ambient temperature to give the ketimines RN═CPh₂ (2a, R = Mes; 2b, R = Ad) in high yield. Kinetic studies for the reaction of 1 with N₃Ad yield activation parameters of ΔH^‡ = +8(±1) kcal/mol and ΔS^‡ = −44(±3) cal/(mol·K). Treatment of 1 with N₂O at low temperature results in clean conversion to the benzophenone complex (dtbpe)Ni(η²-OCPh₂) (5) upon elimination of N₂. The nickel−imido complexes (dtbpe)Ni═NR (4a, R = Mes; 4b, R = Ad) react with N₃Mes and N₃Ad at ambient temperature to give the diazenes RN═NR (6a, R = Mes; 6b, R = Ad) in good yield. B3LYP/6-311+G(d) calculations support a mechanism for all three reactions that features 1,3-dipolar cycloaddition to give five-membered ring (Huisgen) intermediates, followed by N₂ elimination to give the products. Calculated activation parameters for the reaction of (dhpe)Ni═CH₂ (dhpe = 1,2-bis(dihydridophosphino)ethane) with N₃Me compare well with the experimental values.