Diolefin cationic rhodium complexes with sulfur donors. X-ray structure of [Rh(NBD)2(SEt2)]CIO4 |
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| Authors: | A Tiripicchio MTiripicchio Camellini C Claver A Ruiz LA Oro |
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| Institution: | Istituto di Chimica Generale ed Inorganica, Università di Parma, Centro di Studio per la Strutturistica Diffratometrica del C.N.R., Via M. D''Azeglio 85, Parma Italy;Universidad de Barcelona, Departamento de Química Inorgánica, Facultad de Química, Tarragona Spain;Departamento de Química Inorganica, Universidad de Zaragoza, Zaragoza Spain |
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| Abstract: | The preparation and properties of cationic rhodium complexes of the type Rh(diolefin)L2]ClO4 (diolefin COD, NBD; L sulfur donor ligand) are described. Pentacoordinated complexes of general formula Rh(NBD)2L]ClO4 (L SMe2, SEt2, tetrahydrothiophen or trimethylene sulfide) are also reported. The crystal structure of Rh(NBD)2(Set2)]ClO4 has been determined by X-ray methods. The crystals are rhombohedral, space group R3c, with a 14.530(7) Å and α 77.86(5)° (Z = 6). The structure was solved from diffractometer data by direct and Fourier methods and refined by full-matrix least-squares to R = 0.054 for 937 independent observed reflections. In the cationic Rh(NBD)2(SEt2)]+ complex the Rh atom is pentacoordinated, the geometry about the metal being a square pyramid whose base is defined by the midpoints of the olefin bonds from two norbornadiene molecules and the apex is occupied by a sulfur atom of the thioether ligand at a rather long distance Rh?S 2.500(4) Å]. |
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