Elemental Reactions of Vanadium Hydrides (V‐H) toward CO, CO₂, and Alkynes

Comprehensive Summary This study investigates elemental reactions of vanadium hydride {[ Dipp N₂NCH₂C₆H₄]VH}₂{K}₂ ( 1 ) toward CO, CO 2 , and alkynes. Exposure of 1 to CO at −78 °C yielded the dicarbonyl divanadium complex {[ Dipp N₂NBn]V(CO)₂}₂{K}₂ ( 2 ), while heating at 100 °C afforded the CO homologation product {[ Dipp N₂NCH₂C₆H₄]V(THF)}₂(μ‐κ 2 ‐C₂H₂O₂) ( 3 ). Reaction of 1 with CO₂ generated the dinuclear vanadium formate complex {[ Dipp N₂NCH₂C₆H₄]V(HCOO)}₂{K}₂ ( 5 ). Treatment of 1 with methyl phenylpropiolate produced the vanadium enolate complex {[ Dipp N₂NCH₂C₆H₄C(Ph)C(H)COOMe]V}{K(THF)₂} ( 6 ). This work demonstrates new observations of sequential insertion of CO or activated alkynes into both V–H and V‐C Ar bonds, elucidating fundamental reactivity paradigms for vanadium hydrides.