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Diethyl benzoylphosphonate as a ligand
Authors:Chester M Mikulski  William Henry  Louis L Pytlewski  Nicholas M Karayannis
Institution:(1) Department of Chemistry & Physics, Beaver College, 19038 Glenside, Pa., USA;(2) Department of Chemistry, Drexel University, 19104 Philadelphia, Pa., USA;(3) Amoco Chemicals Corporation, 60540 Naperville, Ill., USA
Abstract:Summary Complexes (2 : 1) of diethyl benzoylphosphonate (debp) with 3d metal perchlorates were synthesized and characterized by means of i.r. and electronic spectral, magnetic susceptibility and conductance measurements. In new complexes of the types M(debp)2(OClO3)(OH2)](ClO4) (M = Fe, Co, Zn) and Fe(debp)2(OClO3)(OH2)](ClO4)2, both debp ligands function as bidentate chelating agents, coordinating through the P=O and C=O oxygens. In contrast, in the manganese(II) and nickel(II) complexes, which are of the M(debp)2(OClO3)(OH2)2](ClO4) type, one debp acts as a bidentate chelating ligand, while the second debp is unidentate, coordinating only through the P=O oxygen. Hexacoordination in the new cationic complexes is completed by coordination of aqua and unidentate perchlorato ligands, which are in competition for sites in the inner coordination sphere of the central metal ion with the weak debp ligand. On the other hand, debp, owing to its bulkiness, and especially the presence of the benzoyl substituent, introduces sufficiently severe steric hindrance during coordination. As a result of this, the formation of M(debp)3]n+ tris-chelate cationic complexes with the 3 d metal ions under study does not seem to be possible.
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