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Hydride complexes of ruthenium derived from the heterolytic activation of dihydrogen by amidophosphine complexes

TitleHydride complexes of ruthenium derived from the heterolytic activation of dihydrogen by amidophosphine complexes
Publication TypeJournal Article
Year of Publication2002
JournalComptes Rendus Chimie
Volume5
Pagination451-460
Date PublishedMay
Type of ArticleArticle
Abstract

{The reaction of [NPNH]Ru(eta(3):eta(2)-Cyclooctadienyl) (1) (where [NPNH] = [ PhNHSiMe2CH2P(Ph)CH2SiMe2NPh}), an organometallic mono-amide complex of ruthenium(II), with hydrogen gas (1-4 atm) generates three ruthenium hydride species: [NPNH]RuH (2), [NPNH2]RuH2(C7H8) (3) and [NPNH2]RuH2 (4). All of these complexes result from hydrogenation of the cyclooctadienyl group; complexes 3 and 4 also undergo conversion of the amido linkage into a ruthenium hydride and an amine. Complexes 2 and 3 have been characterized both in solution by NMR spectroscopy and in the solid state by X-ray Diffraction and Infrared Spectroscopy. While 4 was fully characterized in solution by NMR spectroscopy, attempts to recrystallize this material yielded 2; the reaction of 2 with H, does not produce 4. The starting complex I acts as a catalyst precursor for the hydrogenation of imines such as benzylidene aniline; however, none of the isolated hydride species 2, 3 or 4 were active as catalyst precursors.