Bis(mesitylene)vanadium(0), V(mes)2, underwent a two-electron redox process in heptane with CF3SO3H affording the vanadium(II) derivative [V(CF3SO3)2(CF3SO3H)], an example of a co-ordination compound containing both the acid and its conjugated base in its composition. The vanadium(0) complex and CF3CO2H gave a product resulting from a one-electron transfer process, namely [V(mes)2][CF3CO2]. This compound, which dissolves unchanged in neat CF3CO2H–(CF3CO)2O, evolves to the vanadium(II) derivative [H(thf)n][V(CF3CO2)3] (thf = tetrahydrofuran) by addition of tetrahydrofuran. Deprotonation of the vanadium(II) complexes occurs in the presence of thf or heterocyclic nitrogen bases to form the ionic derivatives [HB][VA3], B = thf or a heterocyclic nitrogen base; A = CF3SO3 or CF3CO2. The trifluoroacetato derivative [H(thf)n][V(CF3CO2)3] undergoes methylation with CH2N2 to the vanadium(II) ester adduct [V(CF3CO2)2(CF3CO2CH3)], and is oxidized to the vanadium(III) trifluoroacetato derivatives [V(CF3CO2)3] and [V(CF3CO2)2C14H8O2] by benzoyl peroxide (or dioxygen) and 9,10-phenanthrenedione, respectively.
Synthesis of protonated carboxylato- and trifluoromethanesulfonato derivatives of vanadium(II) by redox reactions on bis(trimethylbenzene)vanadium(0)
CALDERAZZO, FAUSTO;PAMPALONI, GUIDO
1997-01-01
Abstract
Bis(mesitylene)vanadium(0), V(mes)2, underwent a two-electron redox process in heptane with CF3SO3H affording the vanadium(II) derivative [V(CF3SO3)2(CF3SO3H)], an example of a co-ordination compound containing both the acid and its conjugated base in its composition. The vanadium(0) complex and CF3CO2H gave a product resulting from a one-electron transfer process, namely [V(mes)2][CF3CO2]. This compound, which dissolves unchanged in neat CF3CO2H–(CF3CO)2O, evolves to the vanadium(II) derivative [H(thf)n][V(CF3CO2)3] (thf = tetrahydrofuran) by addition of tetrahydrofuran. Deprotonation of the vanadium(II) complexes occurs in the presence of thf or heterocyclic nitrogen bases to form the ionic derivatives [HB][VA3], B = thf or a heterocyclic nitrogen base; A = CF3SO3 or CF3CO2. The trifluoroacetato derivative [H(thf)n][V(CF3CO2)3] undergoes methylation with CH2N2 to the vanadium(II) ester adduct [V(CF3CO2)2(CF3CO2CH3)], and is oxidized to the vanadium(III) trifluoroacetato derivatives [V(CF3CO2)3] and [V(CF3CO2)2C14H8O2] by benzoyl peroxide (or dioxygen) and 9,10-phenanthrenedione, respectively.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
