Oxovanadium alkoxide complexes. Syntheses and crystal structures of (Ph 4P) 2[(VO) 2Cl 4(OR) 2] (R = −CH 3, −CH 2CH 2Cl) and [(VO) 2Cl 2MeC(CH 2OH) (CH 2O) 22

Abstract

The reactions of (Ph 4P) [VO 2Cl 2] in various alcohols yield complexes of the type (Ph 4P) 2[(VO) 2Cl 4(OR) 2] (R=−CH 3( 1), −CH 2CH 2Cl ( 2)). Similarly, the reaction of (BzPh 3P) [VO 2Cl 2] with tris(hydroxymethyl)ethane yields [(VO) 2Cl 2MeC(CH 2OH)(CH 2O) 2 2]∗d2BxPh 3PCl∗d2CH 3OH ( 3∗d2BzPh 3PCl∗d2CH 3OH). The molecular anions of complexes 1 and 2 consist of binuclear units of edge-sharing V(IV) square pyramids. The alkoxy groups bridge the two V(V) sites and the ∗ V=O∗ groups adopt the anti-orientation with respect to the V 2O 2 rhombus of the bridging unit. In contrast, the neutral [(VO) 2Cl 2MeC(CH 2OH)(CH 2O) 2 2] consists of the edge-sharing V(V) octahedra. The tridentate ligands each provide one alkoxy oxygen adopting a bridging mode between V(V) sites, an alkoxy oxygen as a terminal ligand to one V(V) site and an alcohol oxygen donor as a terminal ligand to the other V(V) site. The terminal oxo-groups occupy positions approximately coplanar to the V 2O 2 rhombus of the bridging unit. Crystal data: (Ph 4P) 2[(VO) 2Cl 4(OCH 3) 2]∗d2CH 3OH ( 1∗d2CH 3OH), monoclinic P2 1/n, a = 12.068(2), b = 16.388(3), c = 12.893(3) A ̊ , β = 100.72(2)°, Z =2 . (Ph 4P) 2[(VO) 2Cl 4-(OCH 2CH 2Cl) 2] ( 2), triclinic P l, a = 11.227(2), b = 12.496(2), c = 10.609(2) A ̊ , α = 109.78(2), β = 114.68(3), γ = 85.46(3)°, Z = 1 . [(VO) 2Cl 2MeC(CH 2OH)(CH 2O) 2 2]∗d2BzPh 3PCl∗d2CH 3OH ( 3∗d2BzPh 3PCl∗d2CH 3OH), triclinic P 1, a = 10.361(2), b = 15.762(3), c = 10.125(2) A ̊ , α = 105.72(3), β = 90.02(3), γ = 79.86(3)°, Z = 1 .