η 1 ‐Coordination of Phosphinine C 5 H 5 P and Arsenine C 5 H 5 As to Ruthenium(II) and Osmium(II)

Autor: Greta Heydenrych, Jörg Six, Christoph Elschenbroich, Gernot Frenking, Klaus Harms
Rok vydání: 2008
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2008:3303-3309
ISSN: 1099-0682
1434-1948
Popis: Reductive complexation of RuCl3 and OsCl3 in the presence of phosphinine C5H5P and arsenine C5H5As yields the species trans-Cl2(η1-C5H5E)4MII (M = Ru, E = P, As; M = Os, E = P). trans-Cl2(η1-C5H5As)4Ru constitutes the first arsenine complex of a late transition metal. Further reduction and isolation of the binary complexes (C5H5E)nM0 (n = 2, 4, 5) failed, presumably because of metal–ligand bond cleavage. According to X-ray diffraction analysis, trans-Cl2(η1-C5H5P)4Ru (3) features two pairs of coplanar trans-phosphinine ligands, which adopt eclipsed and staggered orientations, respectively, with regard to the Cl–Ru–Cl backbone. DFT calculations indicate a flat curvature of the potential governing conformational change and predict a structure for 3 that differs from that observed in the crystal. This illustrates the need to include intermolecular Ru–Cl···H hydrogen bonding as a structural director. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Databáze: OpenAIRE
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