Studies on [VCl3(OPMe2Ph)(PMe2Ph)2]. Part 1. Synthesis, structure and reactivity of trans,mer-[VCl3(OPMe2Ph)(PMe2Ph)2], including the X-Ray crystal structure of mer-[VCl3(OPMe2Ph)(Et2PCH2CH2PEt2)]

Abstract

The complex trans,mer-[VCl₃(OPMe₂Ph)(PMe₂Ph)₂] has been prepared and its octahedral structure established by X-ray crystallography with V–Cl_av 2.346(7), V–P 2.547(2), V–O 1.966(5)Å and VOP 157.4(4)°. The phosphine ligands can be displaced by L–L = 2,2′-bipyridine, tetramethylethylene-diamine or Et₂PCH₂CH₂PEt₂ to give [VCl₃(OPMe₂Ph)(L–L)]. The X-ray crystal structure of mer-[VCl₃(OPMe₂Ph)(Et₂PCH₂CH₂PEt₂)] has been determined with V–Cl_av 2.340(11), V–P 2.538(2)Å(trans to Cl), 2.501(2)Å(trans to O), V–O 2.049(4)Å and VOP 134.6(2)°. Other reactions of trans,mer-[VCl₃(OPMe₂Ph)(PMe₂Ph)₂] have been investigated. Protonation with HCl gives [PHMe₂Ph][VCl₄(OPMe₂Ph)], reaction with SiMe₃(S₂CNEt₂) gives [V(S₂CNEt₂)₃] and reduction with MgEtCl in the presence of an excess of Me₂PCH₂CH₂PMe₂ gives trans-[VCl₂(Me₂PCH₂CH₂PMe₂)₂].