Divalent Heteroleptic Ytterbium Complexes – Effective Catalysts for Intermolecular Styrene Hydrophosphination and Hydroamination

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• 作者：Ivan V. Basalov ; Sorin Claudiu Ro?ca ; Dmitry M. Lyubov ; Alexander N. Selikhov ; Georgy K. Fukin ; Yann Sarazin ; Jean-Fran?ois Carpentier ; Alexander A. Trifonov
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 3, 2014
• 年：2014
• 卷：53
• 期：3
• 页码：1654-1661
• 全文大小：346K
• ISSN：1520-510X

文摘

New heteroleptic Yb(II)鈥揳mide species supported by amidinate and 1,3,6,8-tetra-tert-butylcarbazol-9-yl ligands [2-MeOC₆H₄NC(tBu)N(C₆H₃-iPr₂-2,6)]YbN(SiMe₃)₂(THF) (6) and [1,3,6,8-tBu₄C₁₂H₄N]Yb[N(SiMe₃)₂](THF)_n (n = 1 (7), 2 (8)) were synthesized using the amine elimination approach. Complex 6 features an unusual 魏¹-N,魏²-O,畏⁶-arene coordination mode of the amidinate ligand onto Yb(II). Complexes 7 and 8 represent the first examples of lanthanide complexes with 蟺-coordination of carbazol-9-yl ligands. Complexes 6 and 7, as well as the amidinate鈥揧b(II)鈥揳mide [tBuC(NC₆H₃-iPr₂-2,6)₂]YbN(SiMe₃)₂(THF) (5), are efficient precatalysts for the intermolecular hydrophosphination and hydroamination of styrene with diphenylphosphine, phenylphosphine, and pyrrolidine to give exclusively the anti-Markovnikov monoaddition product. For both types of reaction, the best performances were observed with carbazol-9-yl complex 7 (TONs up to 92 and 48 mol/mol at 60 掳C, respectively).