Synthese,Kristallstruktur, Elektronenstruktur,spektroskopische und magnetische Eigenschaften von [VOCl2{P(SiMe3)3}2]: Ein Phosphankomplex mit fehlgeordneter VOCl2-Einheit

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 .