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MOLECULAR DIHYDROGEN AND HYDRIDO DERIVATIVES OF RUTHENIUM(II) COMPLEXES CONTAINING CHELATING FERROCENYL-BASED TERTIARY PHOSPHINE AMINE LIGANDS AND OR MONODENTATE TERTIARY PHOSPHINE-LIGANDS

TitleMOLECULAR DIHYDROGEN AND HYDRIDO DERIVATIVES OF RUTHENIUM(II) COMPLEXES CONTAINING CHELATING FERROCENYL-BASED TERTIARY PHOSPHINE AMINE LIGANDS AND OR MONODENTATE TERTIARY PHOSPHINE-LIGANDS
Publication TypeJournal Article
Year of Publication1992
AuthorsHampton, C, Butler, IR, Cullen, WR, James, BR, Charland, JP, Simpson, J
JournalInorganic Chemistry
Volume31
Pagination5509-5520
Date PublishedDec
Type of ArticleArticle
ISBN Number0020-1669
KeywordsBOND, CARBONYL, D6 COMPLEXES, ETA-2-DIHYDROGEN, EXCHANGE, H-H, HYDROGEN COMPLEXES, palladium, REACTIVITY, TRANSITION-METALS
Abstract

{Reactions of complexes of the type RuCl2(PPh3)(P-N) with H2 are reported, where P-N represents the chelating ferrocene-based ligands (eta-C5H5)Fe(etaC5H3(CHMeNMe2)PR2-1,2) with R = i-Pr (the isoPFA ligand) or Ph (the PPFA ligand). Depending on the solvent(s) used, and absence or presence of added base, RuCl2(PPh3)(isoPFA) (2b) generates the dinuclear eta2-H2 complexes L2(eta2-H2)Ru(eta-Cl)2(eta-H)Ru(H)(PPh3)2 where L2 = isoPFA (complex 3) or L2 = (PPh3)2 (complex 4). n-Butanol solutions of RuCl2(PPh3)(PPFA) (2a) under H-2 also yield 4, as well as Ru(H)Cl2(PPh3)(PPFA.H)(BuOH), a zwitterionic species containing a protonated amine moiety stabilized by coordinated n-BuOH, which is a likely intermediate in heterolytic cleavage of the H-2: the complex RuH(Cl)-PPh3)(isoPFA) (5), together with a hydrido carbonyl species, is isolated from methanol solutions of 2b. Complexes 2b, 3, 4, and 5 are characterized by X-ray crystallography; the mononuclear complexes 2b and 5 are orthorhombic with space groups F2dd and P2(2)2(1)2(1), respectively. For 2b

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