Oxidation of the ruthenium hydride complex (. eta. sup 5 -C sub 5 H sub 5 )Ru(CO)(PPh sub 3 )H: Generation of a dihydrogen complex by oxidatively induced intermolecular proton transfer

Journal Article · Tue Jan 01 00:00:00 EST 1991 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00047a064· OSTI ID:6110071

Ryan, O B; Tilset, M ^[1]; Parker, V D ^[2]

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1. Univ. of Oslo (Norway)
2. Utah State Univ., Logan (United States)

Ruthenium hydride ({eta}{sup 5}-C{sub 5}H{sub 5})Ru(CO)(PPh{sub 3})H (1) undergoes a chemically irreversible oxidation at +0.39 V vs the ferrocene/ferrocenium couple. Oxidation of 1 with ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}Fe{sup +}PF{sub 6}{sup {minus}} (3) in dichloromethane-d{sub 2} yields the known dihydrogen complex ({eta}{sup 5}-C{sub 5}H{sub 5})Ru(CO)(PPh{sub 3})({eta}{sup 2}-H{sub 2}){sup +} (4) as a primary decomposition product. Ferrocenium oxidation of 1 in acetonitrile-d{sub 3} yielded ({eta}{sup 5}-C{sub 5}H{sub 5})Ru(CO)(PPh{sub 3})(NCCD{sub 3}){sup +} (2-d{sub 3}), HRu(CO)(PPh{sub 3})(NCCD{sub 3}){sub 3}{sup +} (5-d{sub 9}), and cyclopentadiene. Cyclopentadiene and 5-d{sub 9} were generated via the prior formation of dihydrogen complex 4. Solutions of independently prepared 4 in acetonitrile-d{sub 3} were observed to decompose to yield some 2-d{sub 3}, but mostly 5-d{sub 9} and cyclopentadiene. The results are discussed in terms of an initial proton transfer from cation radical 1{sup {sm bullet}+} to the Ru center of 1, yielding 4. It is proposed that a reversible, base-catalyzed deprotonation/protonation sequence generates an undetected cationic trans dihydride intermediate from which cyclopentadiene is eliminated.

• OSTI ID: 6110071
• Journal Information: Organometallics; (United States), Vol. 10:1; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
OXIDATION
ACETONITRILE
BORON FLUORIDES
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CYCLOPENTADIENE
ELECTRIC POTENTIAL
ELECTROCHEMICAL CELLS
ELECTROLYSIS
INFRARED SPECTRA
IRON COMPLEXES
LIGANDS
METHYLENE CHLORIDE
NMR SPECTRA
PHOSPHINES
REACTION INTERMEDIATES
VOLTAMETRY
ALKENES
BORON COMPOUNDS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
DIENES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
KINETICS
LYSIS
NITRILES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
POLYENES
REACTION KINETICS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties