Title: Direct observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of sterics
Authors : Frech, Christian M.
Milstein, David
Published in : Journal of the American Chemical Society
Volume(Issue) : 128
Issue : 38
Pages : 12434
Pages to: 12435
Publisher / Ed. Institution : American Chemical Society
Issue Date: 2006
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
Language : English
Subject (DDC) : 540: Chemistry
Abstract: A rare case of directly observed alkyl halide reductive elimination from rhodium is reported. Treatment of the naphthyl-based PCP-type Rh(III) methyl complexes 2a,b [(C10H5(CH2PR2)2)Rh(CH3)(I)] (R = iPr 2a, R = tBu 2b) with CO resulted in facile reductive elimination of methyl iodide in the case of 2b, yielding the Rh(I) carbonyl complex [(C10H5(CH2PR2)2)Rh(CO)] 3b (R = tBu), while the less bulky 2a formed CO adducts and did not undergo reductive elimination, contrary to expectations based on electron density considerations. Moreover, 3b oxidatively added methyl iodide, while 3a did not. CD3I/CH3I exchange studies in the absence of CO indicate that reversible formation of (ligated) methyl iodide takes place in both systems. Subsequently, when CO is present, it displaces methyl iodide in the bulkier tBu system, whereas with the iPr system formation of the Rh(III) CO adducts is favored. Iodide dissociation followed by its attack on the rhodium-methyl group is unlikely.
Departement: Life Sciences and Facility Management
Publication type: Article in scientific Journal
DOI : 10.1021/ja064945d
ISSN: 0002-7863
1520-5126
URI: https://digitalcollection.zhaw.ch/handle/11475/10513
Appears in Collections:Publikationen Life Sciences und Facility Management

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