由 R3P/Al(C6F5)3 受阻路易斯对和 N2O 衍生的自由基离子对引发的 C-H 键活化。
C-H bond activation by radical ion pairs derived from R3P/Al(C6F5)3 frustrated Lewis pairs and N2O.
机构信息
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 3H6.
出版信息
J Am Chem Soc. 2013 May 1;135(17):6446-9. doi: 10.1021/ja402964h. Epub 2013 Apr 19.
Al(C6F5)3/R3P [R = tert-butyl (tBu), mesityl (Mes), naphthyl (Nap)] frustrated Lewis pairs react with N2O to form species having the formula R3P(N2O)Al(C6F5)3, which react with additional alane to generate proposed frustrated radical ion pairs formulated as [R3P·][(μ-O·)(Al(C6F5)3)2] that can activate C-H bonds. For R = tBu, C-H activation of a tBu group affords [tBu2PMe(C(CH2)Me)][(μ-OH)(Al(C6F5)3)2]. In the case of R = Mes, the radical cation salt [Mes3P·][(μ-HO)(Al(C6F5)3)2] is isolated, while for R = Nap, the activation of toluene and bromobenzene gives [(Nap)3PCH2Ph][(μ-OH)(Al(C6F5)3)2] and [(Nap)3PC6H4Br][(μ-HO)(Al(C6F5)3)2], respectively.
三(六氟代戊基)铝/三异丙基膦[R = 叔丁基(tBu)，均三甲苯基(Mes)，萘基(Nap)]受阻路易斯对与 N2O 反应形成化学式为 R3P(N2O)Al(C6F5)3 的物质，该物质与额外的三乙胺反应生成提议的受阻自由基离子对，其化学式为[R3P·][(μ-O·)(Al(C6F5)3)2]，可激活 C-H 键。对于 R = tBu，tBu 基团的 C-H 激活生成 [tBu2PMe(C(CH2)Me)][(μ-OH)(Al(C6F5)3)2]。对于 R = Mes，分离出阳离子盐[Mes3P·][(μ-HO)(Al(C6F5)3)2]，而对于 R = Nap，甲苯和溴苯的活化分别得到[(Nap)3PCH2Ph][(μ-OH)(Al(C6F5)3)2]和[(Nap)3PC6H4Br][(μ-HO)(Al(C6F5)3)2]。
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