Synthesis and characterization of d(0) imido complexes of vanadium. Crystal structure of [V(2,6-(Pr2C6H3N)-Pr-i)(S2CNC4H4)(3)]

Interaction of [V(NR)Cl-3] compounds with 1,2-dimethoxyethane (dme) afforde d [V(NR)Cl-3(dme)] (R = 2,6-(Pr2C6H3)-Pr-i 1a or 1-adamantyl 1b) complexes in a nearly quantitative yield. Compounds 1 are suitable sources for the sy nthesis of other d(0) imidovanadium complexes. Metathesis reactions of 1 wi th the sodium salt of the Klaui's ligand, NaLOEt (L-OEt = (eta-C5H5)Co{P(O) (OEt)(2)}(3)), yielded complexes [V(NR)Cl-2(L-OEt)] (R = 2,6-(Pr2C6H3)-Pr-i 2a or 1-adamantyl 2b). Treatment of 1 with several bidentate monoanionic d ithio-ligands, -S2CR', gave the corresponding imido complexes of general fo rmulation [V(NR)(S2CR')(3)] (for R = 2,6-(Pr2C6H3)-Pr-i; R' = NC4H4 3a, (NP r2)-Pr-i 4, (OPr)-Pr-i 5a or (SPr)-Pr-i 6a; for R = 1-adamantyl; R' = NC4H4 3b, (OPr)-Pr-i 5b or (SPr)-Pr-i 6b). The molecular structure of [V(2,6-(Pr 2C6H3N)-Pr-i)(S2CNC4H4)(3)] 3a has been determined by an X-ray study. Final ly, the reaction of 1a with Na(acac), in a 1:2 molar ratio, produces comple x [V(2,6-(Pr2C6H3N)-Pr-i)Cl(acac)(2)] 7.