Oxidative addition of CH2CI2 to neutral dimeric rhodium diphosphine complexes

被引：10

作者：

Mannu, Alberto ^{[1
]}

Drexler, Hans-Joachim ^{[1
]}

Thede, Richard ^{[2
]}

Ferro, Monica ^{[1
,3
]}

Baumann, Wolfgang ^{[1
]}

Rueger, Julia ^{[1
]}

Heller, Detlef ^{[1
]}

机构：

[1] Univ Rostock LIKAT Rostock, Leibniz Inst Katalyse eV, Albert Einstein Str 29a, D-18059 Rostock, Germany

[2] Ernst Moritz Arndt Univ Greifswald, Inst Biochem, Felix Hausdorff Str 4, D-17487 Greifswald, Germany

[3] Politecn Milan, Dept Chem Mat & Chem Engn G Natta, Piazza L da Vinci 32, I-20133 Milan, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2018年 / 871卷

关键词：

Oxidative addition; Rhodium; Diphosphine ligand; CH2CI2; activation; Kinetics; CATALYZED ASYMMETRIC HYDROGENATION; METHYLENE-BRIDGED COMPOUNDS; TRANSITION-METAL-COMPLEXES; C-CL-ACTIVATION; TERMINAL ALKYNES; ALPHA; BETA-UNSATURATED NITRILES; PHOSPHINE COMPLEXES; OXABICYCLIC ALKENES; CARBOXYLIC-ACIDS; CARBONYL SOURCE;

D O I：

10.1016/j.jorganchem.2018.07.011

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Neutral dimeric rhodium diphosphine complexes are often employed as catalytic precursors in the presence of the solvent CH2Cl2. The possibility of a collateral reaction between the solvent and the catalytic precursor is never considered as the activation of CH2Cl2 by [Rh-2(PP)(2)(mu(2) -CI)(2)]complexes is reputed difficult and uncommon. Herein we report the easy formation of three neutral dimeric Rh(III) complexes containing DPPP, DPPB and TangPhos through CH2Cl2 activation as an extension of the few examples reported so far. The system [Rh-2(DPPP)(2)(mu(2) -CI)(2)]/CH2Cl2 has been selected for a detailed mechanistic investigation. Kinetic studies based on P-31 NMR monitoring combined with metathesis experiments reveal the fundamental role of a 14-electron intermediate [Rh(PP)CI], which is involved in the CH2Cl2 activation. (C) 2018 Elsevier B.V. All rights reserved.

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页码：178 / 184

页数：7

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