Vanadium phenoxide complexes with oxide, nitride or hydrazide co-ligands: preparation and crystal structures of [V(OC6H3Pr2i-2,6)(3-)NLi(C4H8O)(3)], [{VO2(OC6H3Pr2i-2,6)(2)}{mu-Li(C4H8O)(2)}(2)] and [V(NNMe2)(OC6H3Pr2i-2,6)(3)]

Treatment of [V(OC6H3Pr2i-2,6)(2)(mu-OC6H3Pr2i-2,6)(2)Li(C4H8O)] (1) with S iMe3N3 in hexane gives two products. The first, [V(OC6H3Pr2i-2,6)(3)NLi(C4H 8O)3] (2), contains the V-N-Li linkage and has essentially tetrahedral vana dium (d(V-N) 1.565(5), d(Li-N) 2.061(13), d(V-OC6H3Pr2i-2,6) (average) 1.82 8(4)Angstrom; angle (Li-N-V) 164.0(5)degrees). The second product, [{VO2(OC 6H3Pr2i-2,6)(2)}2{mu-Li(C4H8O)(2)}(2)] (3), which is formed by adventitious entry of water into the reaction solution, contains an eight-membered ring structure formed by two Li(thf)(2) groups bridging two tetrahedral VO2(OC6 H3Pr2i-2,6)(2) units (d(V-O) (range) 1.557(10)-1.669(9), (d(V-OC6H3Pr2i-2.6 ) (average) 1.803(12), d(Li-O) (vanadium) (average) 1.91(7) Angstrom). The hydrazide complex [V(NNMe2)(OC6H3Pr2i-2,6)(3)] (4) has been synthesised by treatment of the dianion [{VCl3}(2){mu-NNMe2)(3)](2-) with Li[OC6H3Pr2i-2,6 ]. Compound 4 has distorted tetrahedral geometry at vanadium, (d(V-N) 1.653 (3), d(V-OC6H3Pr2i-2,6) (average) 1.793(3) d(N-N) 1.311(4) Angstrom, and an gle (V-N-N) 175.8(3)degrees. Compound 4 reacts with N(CH2CH2SH)(3) to give [V(NNMe2){N(CH2CH2S)(3)}]. Spectroscopic and other physical data for these complexes are presented and discussed. (C) 1999 Elsevier Science S.A. All r ights reserved.