Michel O. Albers

The chemistry of cyclopentadienyl-ruthenium and -osmium complexes. II: Novel mononuclear cyclopentadienylruthenium complexes containing aromatic amine ligands: a facile synthetic route

Abstract The reaction of [(η-C 5 H 4 R)Ru[η-C 8 H 12 )Cl] (R = H, Me; C 8 H 12 = cycloocta-1,5-diene) with bidentate amine ligands has been used to prepare a series of novel cyclopentadienylruthenium(II) diamine complexes, [(η-C 5 H 4 R)Ru(diamine)Cl] (R = H, Me; diamine = 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenathroline, 5-nitro-1,10-phenanthroline, 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine. These complexes have been completely characterized by microanalysis, 1 H and 13 C NMR spectroscopy, 1 H/ 13 C heteronuclear shift correlation spectroscopy, and visible spectroscopy.

The preparation and some reactions of chloro(η4-cycloocta-1,5-diene)(η5-cyclopentadienyl)ruthenium(II): A versatile, new synthetic precursor for cyclopentadienylruthenium(II) chemistry

Abstract Facile substitution of the cyclooctadiene and/or chloro ligands in [(η 5 -C 5 H 5 )Ru(C 8 H 12 Cl] (C 8 H 12 = cycloocta-1,5-diene) under mild reaction conditions provides high yield synthetic routes to a range of new neutral and cationic cyclopentadienylruthenium(II) complexes.

Dimeric ruthenium(II) complexes containing bridging carboxylato and aquo ligands. The crystal structure of μ-aquobis(μ-trifluoroacetato)bis[(η4-cycloocta-1,5-diene)(trifluoroacetato)ruthenium(II)]

Abstract Protonation of [Ru(μ 3 -C 3 H 4 R) 2 (C 8 H 12 )] (R = H, Me; C 8 H 12 = cycloocta-1,5-diene) with haloacetic acids gives the dimers [Ru 2 (C 8 H 12 ) 2 (O 2 CR′) 2 (μ-O 2 CR′) 2 -(μ-OH 2 )] (R′ = CF 3 , CCl 3 and CH 2 Cl), which are precursors for a range of monomeric and dimeric ruthenium carboxylate complexes. The complex [Ru 2 (C 8 H 12 ) 2 -(O 2 CCF 3 ) 2 (μ-O 2 CCF 3 ) 2 (μ-OH 2 )] has been characterized by X-ray analysis.

The hydrogenation of alkenes and alkynes in the presence of [Ru(COD)(PMe2Ph)3+: a comparison with the [RuH(PMe2Ph)5]+ alkyne hydrogenation catalyst

Abstract [RuH(COD)(PMe 2 Ph) 3 ] [PF 6 ] (COD = 1,5-cyclooctadiene), A, a phos-phine-deficient analogue of the alkyne hydrogenation catalyst [RuH(PMe 2 Ph) 5 ]PF 6 ], has been observed to hydrogenate both alkynes and alkenes under mild conditions (1 atm P , 25 °C). Reactions are hydrogen diffusion controlled. Addition of up to 2 equiv PMe 2 Ph to reaction solutions containing A results in a change in the catalytic behavior of the solutions such that a decrease in the alkene hydrogenation rate occurs. On addition of 2 equiv PMe 2 PH, only the hydrogenation of alkynes is observed. Mechanistic features of the catalysed hydrogenation of alkenes and alkynes in the presence of A and related species are discussed.

The chemistry of cyclopentadienyl-ruthenacyclopentatrienes: novel carbon monoxide and isocyanide insertion reactions in [η5-C5H5)Ru(η4-C5Ph2H2NBut)Br]

Abstract Reaction of the novel ruthenacyclopentatriene [(η5-C5H5)Ru(C4Ph2H2)Br] (1) with isocyanides gives the imino-2,5-diphenylcyclopentadiene complexes [(η5-C5H5Ru(η4-C5Ph2H2NR)Br] (2, R = Me, Et, Cy, t-Bu, 2,6-Me2C6H3); a novel fluxional process involving phenyl substituent rotation and imino nitrogen inversion has been identified for 2 (R = t-Bu, 2,6-Me2C6H3), the interpretation of which is supported by the X-ray crystal structure determination of 2 (R = t-Bu).

The systematic synthesis of novel bridged diruthenium cation containing cyclopentadienyl and bidentate amine ligands. The crystal and molecular structure of [{(η5-C5H5)RU)1,10-phenanthroline)}2(μ-dppm)][PF6)2·CH2Cl2 (dppm = bis(diphenylphosphino)methane)

Abstract The labile cation [(η 5 -C 5 H 5 )Ru(1,10-phen)(ethanol)] + (phen = phenanthroline) undergoes a substitution reaction with bis(diphenylphosphino)methane (dppm) to give [(η 5 -C 5 H 5 )Ru(1,10-phen)(η 1 -dppm)] + and [{(η 5 -C 5 H 5 )Ru(1,10-phen)} 2 (η-dppm)] 2+ , and with [η 5 -C 5 H 5 )Ru(PPh 3 )(η 1 -dppm)Cl]. [(η 5 -C 5 H 5 )Ru(dppm)(η 1 -dppm)]PF 6 and [Fe(CO) 4 (η 1 -dppm)] to give unsymmetrical μ-dppm complexes. The X-ray crystal structure of [{η 5 -C 5 H 5 )Ru(1,10-phen)} 2 (μ-dppm)](PF 6 ) 2 ·CH 2 Cl 2 has been determined.