Vanadium(V/IV) Oxido Complexes: Potential as Bases in Frustrated Lewis Pairs

Abstract Frustrated Lewis Pairs (FLP) have found exciting access in catalysis and small molecule activation. Here, we describe the potential of two vanadium(V) oxido complexes with monoanionic bidentate N,O donors, [VOCl(L CF3 ) 2 ] ( 1 a ), [VOCl(L H ) 2 ] ( 1 b ) as bases in FLPs. Upon reaction of 1 a with the Lewis acid B(C 6 F 5 ) 3 the FLP [VOCl(L CF3 ) 2 ]/B(C 6 F 5 ) 3 ( 1 a /B(C 6 F 5 ) 3 ) was observed. Addition of Ph 3 SiH led to the reduction of V V to V IV under formation of the adduct [V{OB(C 6 F 5 ) 3 }(L CF3 ) 2 ] ( 2 a ) while FLP reactivity was not observed. Dissolving 2 a in CH 3 CN leads to the V IV oxido complex, [VO(L CF3 ) 2 ] ( 3 a ). In contrast, when 1 b was reacted with B(C 6 F 5 ) 3 , a V IV oxido complex [VO(L H ) 2 ] ( 3 b ) was obtained. Upon addition of B(C 6 F 5 ) 3 to 3 b no reaction leading to the expected adduct such as 2 a could be observed. Only few crystals deriving from a disproportion reaction could be identified as an adduct dimer [V{OB(C 6 F 5 ) 3 }L H (μ‐O)] 2 . While FLP reactivity could not be found yet with the described systems, the redox labile nature and versatility of the metal complexes are demonstrated.