Synthese,Kristallstruktur, Elektronenstruktur,spektroskopische und magnetische Eigenschaften von [VOCl2{P(SiMe3)3}2]: Ein Phosphankomplex mit fehlgeordneter VOCl2-Einheit |
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Authors: | Winfried Plass Wolfgang Schwarz |
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Abstract: | Synthesis, Crystal Structure, Electronic Structure, Spectroscopic and Magnetic Properties of [VOCl2{P(SiMe3)3}2]: A Phosphane Complex with a Disordered VOCl2 Group VOCl3 reacts with P(SiMe3)3 to form blue green crystals of [VOCl2{P(SiMe3)3}2] ( 1 ). The X-ray crystal structure analysis of 1 (cubic space group P213: a = 1541.4(1) pm, Z = 4) reveals a slightly distorded trigonal bipyramidal coordination environment for the disordered vanadium(IV) center. Density functional calculations on the compound [VOCl2{P(SiH3)3}2] ( 2 ) are in accord with this observation. 1 has been characterized by ESR, vibrational (IR and Raman) and electronic absorption spectroscopy and magnetic measurements. The ESR spectra of 1 in a toluene solution (293 K and frozen solution at 6 K) exhibit hyperfine interactions of the unpaired electron with the 51V center (I = 7/2) and the 31P centers (I = 1/2) of the two equivalent phosphane ligands. The ligand-field transitions of the VOCl2{P}2 chromophore observed in the electronic absorption spectrum have been assigned on the basis of density functional calculations on 2 . |
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Keywords: | Crystal Structure Electronic Structure Spectroscopic Data Tris(trimethylsilyl)phosphane Complexes Vanadium |
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