Oxovanadium alkoxide complexes. Syntheses and crystal structures of (Ph4P)(2)[(VO)(2)Cl-4(OR)(2)] (R=-CH3,-CH2CH2Cl) and [(VO)(2)Cl-2{MeC(CH2OH)(CH2O)(2)}(2)]

The reactions of (Ph4P) [VO2Cl2] in various alcohols yield complexes of the type (Ph4P)(2)[(VO)(2)Cl-4(OR)(2)] (R =-CH3 (1),-CH2CH2Cl (2)). Similarly, the reaction of (BzPh(3)P)[VO2Cl2] with tris(hydroxymethyl) ethane yields [(VO)(2)Cl-2(MeC(CH2OH) (CH2O)(2)}(2)]. 2BzPh(3)PCl . 2CH(3)OH (3 . 2BzPh(3)PCl . 2CH(3)OH). 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 (V2O2} rhombus of the bridging unit. In contrast, the neutral [(VO)(2)Cl-2(MeC(CH2OH) (CH2O)(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 ore-groups occupy positions approximately coplanar to the (V2O2} rhombus of the bridging unit. Crystal data: (Ph4P)(2)[(VO)(2)Cl-4(OCH3)(2)]. 2CH(3)OH (1 . 2CH(3)OH), monoclinic P2(1)/n, a=12.068(2), b=16.388(3), c=12.893(3) Angstrom, beta=100.72(2)degrees, Z=2. (Ph4P)(2)[(VO)(2)Cl-4- (OCH2CH2Cl)(2)] (2), triclinic P (1) over bar, a = 11.227(2), b = 12.396(2), c = 10.609(2) Angstrom, alpha = 109.78(2), beta = 114.68(3), gamma= 85.46(3)degrees, Z= 1. [(VO)(2)Cl-2(MeC(CH2OH)(CH2O)(2)](2)]. 2BzPh(3)PCl . 2CH(3)OH (3 . 2BzPh(3)PCl . 2CH(3)OH), triclinic P (1) over bar, a=10.316(2), b=15.762(3), c=10.125(2) Angstrom, alpha=105.72(3), beta= 90.02(3), gamma= 79.86(3)degrees, Z=1.