Abstract
The polymer [RuCl 2(diene)] n undergoes bridge cleavage reaction with amines giving, at temperatures dependant on the nature of the diene moiety, the monomer [RuClH(diene)(amine) 2]. The crystal structure of the compound [RuClH(cod)(pip) 2] has been determined from three dimensional X-ray data. The complex crystallizes in space group Pmcn of the orthorhombic system, a 16.808(4), b 11.520(2), c 9.744(2) Å D m 1.44 D c 1.46 g cm −3; Z 4. The structure was solved by standard heavy atom methods and has been refined by least squares to a conventional R factor of 0.039 based on 3280 refections. The complex has a crystallographically C s imposed symmetry. The coordination geometry around the ruthenium atom is octahedrally distorted with cis amine ligands, the chloro and the hydrido ligands being trans to each other and the cyclooctadiene moiety bound through the two double bonds. The CC distances of the olefinic bonds are longer (1.394(4) Å) than was to be expected according to the Dewar—Chatt—Duncanson model. Principal bond lengths are: RuH 1.57(4); RuCl 2.555(1) (demonstrating a high structural trans influence of the hydrido ligand); RuN, 2.240(2) Å. An order of increasing structural trans influence for RuCl distances is proposed. In the IR spectrum ν(RuH) was observed at 2040 cm −1. Decomposition of the complexes in chlorinated solvents prevented NMR studies.
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