<I>cis</I>-Tricarbonylbistriphenylphosphinemanganese and the Related Compounds

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概要

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• Tricarbonyl-methylcyclopentadienylmanganese(I) (I) gives two manganese carbonyl triphenylphosphine compounds when treated with triphenylphosphine in the presence of a sodium dispersion, with tetrahydrofuran used as the solvent. One compound is a known diamagnetic (CH<SUB>3</SUB>-C<SUB>5</SUB>H<SUB>4</SUB>)Mn(CO)<SUB>2</SUB>(PPh<SUB>3</SUB>)(II) (38% yield) formed by a ligand substitution reaction without any change in the oxidation number of the central manganese (+1). The other compound is a novel paramagnetic manganese(0) compound, <I>cis</I>-Mn(CO)<SUB>3</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB> (III) (25% yield), which may be formed by a reductive phosphination reaction. A <I>cis</I> trigonal bipyramidal configuration, as in the case reported for Fe(CO)<SUB>3</SUB>(<I>o</I>-(AsMe<SUB>2</SUB>)<SUB>2</SUB>C<SUB>6</SUB>H<SUB>4</SUB>), is proposed for III on the basis of the results of infrared spectroscopy. The compound III gives the following derivatives: BrMn(CO)<SUB>3</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB>, VI, CH<SUB>3</SUB>Mn(CO)<SUB>3</SUB>(P-Ph<SUB>3</SUB>)<SUB>2</SUB>, VII, and Mn(CO)<SUB>3</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB>·1/2· CHCl<SUB>3</SUB>, VIII.

• 公益社団法人 日本化学会の論文

著者

• Nakayama Hiroaki

  Department Of Bacteriology Faculty Of Medical Sciences Kyushu University

• Nakayama Hiroaki

  Department of Chemistry, Faculty of Science, The University of Tokyo

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