Highly efficient hydrosilylation of alkenes by organoyttrium catalysts with sterically demanding amidinate and guanidinate ligands

被引：100

作者：

Ge, Shaozhong ^{[1
]}

Meetsma, Auke ^{[1
]}

Hessen, Bart ^{[1
]}

机构：

[1] Univ Groningen, Ctr Catalyt Olefin Polymerizat, Stratingh Inst Chem, NL-9747 AG Groningen, Netherlands

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 13期

关键词：

D O I：

10.1021/om800032g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The sterically demanding guanidine ArNHC(Me(2))NAr (Ar = 2,6-diisopropylphenyl, HL) reacts with Y(CH(2)SiMe(3))(3)(THF)(2) to give the yttrium dialkyl complex (L)Y(CH(2)SiMe(3))(2)(THF) (1), which was structurally characterized. Electronic interaction of the -NMe(2) group with the conjugated ligand backbone can be inferred from structural and spectroscopic data. The new yttrium guanidinate complex 1 and its related amidinate analogue [PhC(NAr)(2)]Y(CH(2)SiMe(3))(2)(THF) (2) are highly active and selective catalysts for alkene hydrosilylation with PhSiH(3) (tof > 600 h(-1) at 23 degrees C). For unfunctionalized olefins, full selectivity toward anti-Markovnikov products was obtained. The more electron donating guanidinate ligand affords the highest activities with heteroatom-functionalized substrates.

引用

页码：3131 / 3135

页数：5

共 42 条

[1] The coordination chemistry of guanidines and guanidinates [J].

Bailey, PJ ;

Pace, S .

COORDINATION CHEMISTRY REVIEWS, 2001, 214 :91-141

[2] One ligand fits all: Cationic mono(amidinate) alkyl catalysts over the full size range of the group 3 and lanthanide metals [J].

Bambirra, S ;

Bouwkamp, MW ;

Meetsma, A ;

Hessen, B .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (30) :9182-9183

[3]

Bambirra S, 2006, DALTON T, P1157, DOI 10.1039/b512135c

[4] Yttrium alkyl complexes with a sterically demanding benzamidinate ligand: synthesis, structure and catalytic ethene polymerisation [J].

Bambirra, S ;

van Leusen, D ;

Meetsma, A ;

Hessen, B ;

Teuben, JH .

CHEMICAL COMMUNICATIONS, 2003, (04) :522-523

[5] Mono(amidinate) yttrium alkyl complexes: The effect of ligand variation on ethene polymerization catalysis [J].

Bambirra, Sergio ;

Otten, Edwin ;

van Leusen, Daan ;

Meetsma, Auke ;

Hessen, Bart .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2006, 632 (12-13) :1950-1952

[6] Lanthanum tribenzyl complexes as convenient starting materials for organolanthanum chemistry [J].

Bambirra, Sergio ;

Meetsma, Auke ;

Hessen, Bart .

ORGANOMETALLICS, 2006, 25 (14) :3454-3462

[7]

BARKER J, 1994, COORDIN CHEM REV, V137, P403

[8]

Beurskens P.T., 1999, DIRDIF99

[9] Second generation N-heterocyclic carbene-Pt(0) complexes as efficient catalysts for the hydrosilylation of alkenes [J].

Buisine, O ;

Berthon-Gelloz, G ;

Brière, JF ;

Stérin, S ;

Mignani, G ;

Branlard, P ;

Tinant, B ;

Declercq, JP ;

Markó, IE .

CHEMICAL COMMUNICATIONS, 2005, (30) :3856-3858

[10] SELECTIVE SYNTHESES WITH ORGANOMETALLICS .11. AN EFFICIENT SYNTHESIS OF ALPHA,BETA-UNSATURATED ALDEHYDES BY A 4-CARBON UNIT EXTENSION OF GRIGNARD-REAGENTS [J].

CLOUX, R ;

SCHLOSSER, M .

HELVETICA CHIMICA ACTA, 1984, 67 (06) :1470-1474

← 1 2 3 4 5 →