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

被引:66
作者
Basalov, Ivan V. [1 ]
Rosca, Sorin Claudiu [2 ]
Lyubov, Dmitry M. [1 ]
Selikhov, Alexander N. [1 ]
Fukin, Georgy K. [1 ]
Sarazin, Yann [2 ]
Carpentier, Jean-Francois [2 ]
Trifonov, Alexander A. [1 ]
机构
[1] Russian Acad Sci, GA Razuvaev Inst Organometall Chem, Nizhnii Novgorod, Russia
[2] Univ Rennes 1, CNRS, UMR 6226, Inst Sci Chim Rennes, Rennes, France
基金
俄罗斯基础研究基金会;
关键词
HIGHLY REACTIVE ORGANOLANTHANIDES; MIXED-LIGAND; INTRAMOLECULAR HYDROPHOSPHINATION/CYCLIZATION; METAL-CATALYSTS; CHEMISTRY; POLYMERIZATION; LANTHANIDE; ALKENES; SAMARIUM(II); SCOPE;
D O I
10.1021/ic4027859
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
New heteroleptic Yb(II)-amide species supported by amidinate and 1,3,6,8-tetra-tert-butylcarbazol-9-yl ligands [2-MeOC6H4NC(tBu)N-(C6H3-iPr(2)-2,6)]YbN(SiMe3)(2)(THF) (6) and [1,3,6,8-tBu(4)C(12)H(4)N]Yb[N(SiMe3)(2)](THF)(n) (n = 1 (7), 2 (8)) were synthesized using the amine elimination approach. Complex 6 features an unusual kappa(1)-N,kappa(2)-O,eta(6)-arene coordination mode of the amidinate ligand onto Yb(II). Complexes 7 and 8 represent the first examples of lanthanide complexes with pi-coordination of carbazol-9-yl ligands. Complexes 6 and 7, as well as the amidinate-Yb(II)-amide [tBuC(NC6H3-iPr(2)-2,6)(2)]YbN(SiMe3)(2)(THF) (5), are efficient pre-catalysts 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 degrees C, respectively).
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页码:1654 / 1661
页数:8
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