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η 1 ‐Coordination of Phosphinine C 5 H 5 P and Arsenine C 5 H 5 As to Ruthenium(II) and Osmium(II)
Author(s) -
Elschenbroich Christoph,
Six Jörg,
Harms Klaus,
Frenking Gernot,
Heydenrych Greta
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200701226
Subject(s) - chemistry , osmium , ruthenium , crystallography , crystal structure , transition metal , ligand (biochemistry) , metal , hydrogen bond , x ray crystallography , stereochemistry , intermolecular force , reductive elimination , molecule , diffraction , catalysis , biochemistry , physics , receptor , organic chemistry , optics
Reductive complexation of RuCl 3 and OsCl 3 in the presence of phosphinine C 5 H 5 P and arsenine C 5 H 5 As yields the species trans ‐Cl 2 (η 1 ‐C 5 H 5 E) 4 M II (M = Ru, E = P, As; M = Os, E = P). trans ‐Cl 2 (η 1 ‐C 5 H 5 As) 4 Ru constitutes the first arsenine complex of a late transition metal. Further reduction and isolation of the binary complexes (C 5 H 5 E) n M 0 ( n = 2, 4, 5) failed, presumably because of metal–ligand bond cleavage. According to X‐ray diffraction analysis, trans ‐Cl 2 (η 1 ‐C 5 H 5 P) 4 Ru ( 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)