Synthesis and characterization of d0 imido complexes of vanadium. Crystal structure of [V(2,6-iPr2C6H3N)(S2CNC4H4)3]

Abstract

Interaction of [V(NR)Cl₃] compounds with 1,2-dimethoxyethane (dme) afforded [V(NR)Cl₃(dme)] (R = 2,6-ⁱPr₂C₆H₃ 1a or 1-adamantyl 1b) complexes in a nearly quantitative yield. Compounds 1 are suitable sources for the synthesis of other d⁰ imidovanadium complexes. Metathesis reactions of 1 with the sodium salt of the Kläui’s ligand, NaL_OEt (L_OEt = (η-C₅H₅)Co{P(O)(OEt)₂}₃), yielded complexes [V(NR)Cl₂(L_OEt)] (R = 2,6-ⁱPr₂C₆H₃ 2a or 1-adamantyl 2b). Treatment of 1 with several bidentate monoanionic dithio-ligands, ^–S₂CR′, gave the corresponding imido complexes of general formulation [V(NR)(S₂CR′)₃] (for R = 2,6-ⁱPr₂C₆H₃; R′ = NC₄H₄ 3a, NⁱPr₂ 4, OⁱPr 5a or SⁱPr 6a; for R = 1-adamantyl; R′ = NC₄H₄ 3b, OⁱPr 5b or SⁱPr 6b). The molecular structure of [V(2,6-ⁱPr₂C₆H₃N)(S₂CNC₄H₄)₃] 3a has been determined by an X-ray study. Finally, the reaction of 1a with Na(acac), in a 1∶2 molar ratio, produces complex [V(2,6-ⁱPr₂C₆H₃N)Cl(acac)₂] 7.