Proton induced coupling reactions in dinuclear σ-alkynyl-μ-methylene-rhodium complexes

被引：1

作者：

Castro, A ^{[1
]}

Maitlis, PM ^{[1
]}

Turner, ML ^{[1
]}

Mann, BE ^{[1
]}

Adams, H ^{[1
]}

机构：

[1] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 663卷 / 1-2期

关键词：

rhodium complexes; mu-methylene ligand; carbon-carbon bond formation;

D O I：

10.1016/S0022-328X(02)01964-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Addition of two equivalents of HBF4 to suspensions of the di-alkynyl-di-mu-methylene-dirhodium complexes [(C5Me5)(2)Rh-2(mu-CH2)(2)(C2R)(2)] (2, R = Ph; 3, R = p-C6H4Me) (prepared from the chloro-complex [(C5Me5)(2)Rh-2(mu-CH2)(2)Cl-2] (1), and RC2MgCl), gave the unexpected products syn- and anti -[(C5Me5)(2)Rh-2(mu-eta(5), eta(5')-{XC6H4CH(CH2)CC(CH2)CHC6H4X}][BF4](2) (4, X = H; and 5, X = p-Me). The solid-state structure of syn-5, determined by single crystal X-ray diffraction, was shown to contain a hydrocarbon skeleton of two linked eta(5)-allylbenzenes. Complexes 4 and 5 underwent a dynamic process in solution; this was examined by VT-NMR spectroscopy for 5 and was shown to involve eta(5)-/eta(3)-/eta(5)-migration of the allylbenzene fragment, with a free energy of activation of 62 U mol(-1). The complexes 2 and 3 reacted with HCl to give I and RC2H. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：145 / 150

页数：6

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