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

被引：65

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

来源：

INORGANIC CHEMISTRY | 2014年 / 53卷 / 03期

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).

引用

页码：1654 / 1661

页数：8

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