Vanadium phenoxide complexes with oxide, nitride or hydrazide co-ligands: preparation and crystal structures of [V(OC 6H 3Pr i2-2,6) 3NLi(C 4H 8O) 3], [{VO 2(OC 6H 3Pr i2-2,6) 2} 2{μ-Li(C 4H 8O) 2} 2] and [V(NNMe 2)(OC 6H 3Pr i2-2,6) 3

Abstract

Treatment of [V(OC 6H 3Pr i 2-2,6) 2(μ-OC 6H 3Pr i 2-2,6) 2Li(C 4H 8O)] ( 1) with SiMe 3N 3 in hexane gives two products. The first, [V(OC 6H 3Pr i 2-2,6) 3NLi(C 4H 8O) 3] ( 2), contains the V–N–Li linkage and has essentially tetrahedral vanadium ( d(V–N) 1.565(5), d(Li–N) 2.061(13), d(V–OC 6H 3Pr i 2-2,6) (average) 1.828(4) Å; angle (Li–N–V) 164.0(5)°). The second product, [{VO 2(OC 6H 3Pr i 2-2,6) 2} 2{μ-Li(C 4H 8O) 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 VO 2(OC 6H 3Pr i 2-2,6) 2 units ( d(V–O) (range) 1.557(10)–1.669(9), d(V–OC 6H 3Pr i 2-2,6) (average) 1.803(12), d(Li–O) (vanadium) (average) 1.91(7) Å). The hydrazide complex [V(NNMe 2)(OC 6H 3Pr i 2-2,6) 3] ( 4) has been synthesised by treatment of the dianion [{VCl 3} 2{μ-NNMe 2) 3] 2− with Li[OC 6H 3Pr i 2-2,6]. Compound 4 has distorted tetrahedral geometry at vanadium, ( d(V–N) 1.653(3), d(V–OC 6H 3Pr i 2-2,6) (average) 1.793(3) d(N–N) 1.311(4) Å, and angle (V–N–N) 175.8(3)°). Compound 4 reacts with N(CH 2CH 2SH) 3 to give [V(NNMe 2){N(CH 2CH 2S) 3}]. Spectroscopic and other physical data for these complexes are presented and discussed.