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 04:00:00 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), Journal Name: Organometallics; (United States) Vol. 10:1; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

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