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Serendipitous syntheses of Rh(H)(2)Cl(PRPh2)(3) complexes, and their crystal structures, where R = Me, Cy (cyclohexyl)

TitleSerendipitous syntheses of Rh(H)(2)Cl(PRPh2)(3) complexes, and their crystal structures, where R = Me, Cy (cyclohexyl)
Publication TypeJournal Article
Year of Publication2008
AuthorsLorenzini, F, Patrick, BO, James, BR
JournalInorganica Chimica Acta
Volume361
Pagination2123-2130
Date PublishedMay
Type of ArticleArticle
ISBN Number0020-1693
KeywordsCRYSTALLOGRAPHY, ETHYLENE, EXCHANGE, HOMOGENEOUS CATALYTIC HYDROGENATION, hydride, hydride complexes, NMR, PARAHYDROGEN-INDUCED POLARIZATION, PHOSPHINE COMPLEXES, rhodium, RHODIUM(I), SPECTROSCOPY, TERTIARY PHOSPHINES, WATER, WILKINSONS CATALYST
Abstract

Reactions of RhCl(cod)(THP) (cod = 1,5-cyclooctadiene; THP = P(CH2OH)(3)) with PMePh2 or PCyPh2 (Cy = cyclohexyl) in acetone/MeOH solution under H-2 surprisingly form the complexes cis,mer-Rh(H)Cl-2(PRPh2)(3) (R = Me or Cy); both complexes are characterized by crystallography (the first structures in which the hydride ligands of such dihydrido-chloro-trisphosphine complexes have been located), and by detailed H-1 and P-31 NMR spectroscopy. The key role of the THP in the observed chemistry is discussed. (C) 2007 Elsevier B.V. All rights reserved.

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