H. Klein, R. Beck, U. Flörke
Apr 1, 2003
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0
Influential Citations
33
Citations
Journal
European Journal of Inorganic Chemistry
Abstract
Cyclometalation in the aliphatic ring occurs in the reaction between [CoCH3(PMe3)4] and 5-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthalene to give [{8-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)}tris(trimethylphosphane)cobalt] (1), containing a five-membered metallacycle as shown in the molecular structure. While 1-(diphenylphosphanyl)naphthalene reacts accordingly, affording [{8-(diphenylphosphanyl)naphthyl-(C1,P)}tris(trimethylphosphane)cobalt] (2), 2-(diphenylphosphanyl)biphenyl yields ortho-metalated [{2-(diphenylphosphanyl)-3-phenylphenyl-(C1,P)}tris(trimethylphosphane)cobalt] (3), containing a four-membered metallacycle. 1-(Diphenylphosphanyl)-8-methylnaphthalene is metalated in the aliphatic substituent to form [{[8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris(trimethylphosphane)cobalt] (4). The molecular structure shows a trigonal-bipyramidal configuration of the cobalt atom accommodating a six-membered metallacycle. 2-(Diphenylphosphanyl)styrene replaces two trimethylphosphane ligands to give [{2-(diphenylphosphanyl)styrene-(C,C-η2,P)}methylbis(trimethylphosphane)cobalt] (5), avoiding metalation. Replacement of equatorial trimethylphosphane in compounds 1−3 by ethene gives π-ethene complexes 6−8. In the molecular structure of 7 the C−C vector of the π-ethene ligand is arranged in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, compound 2 forms a monocarbonyl complex 9, in which an equatorial carbonyl ligand is found in the molecular structure. Iodomethane transforms 2 into pentacoordinate [{2-(diphenylphosphanyl)naphthyl-(C1,P)}iodobis(trimethylphosphane)cobalt] (10) with retention of the metallacycle. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003