In the paper, we have studied the mixed-valence isopolyanion by cyclic voltammogram, in-situ UV-Visible-Near-IR and FTIR spectroelectrochemical methods in aprotic medium,such as methylene chloride.A number of hetero-...In the paper, we have studied the mixed-valence isopolyanion by cyclic voltammogram, in-situ UV-Visible-Near-IR and FTIR spectroelectrochemical methods in aprotic medium,such as methylene chloride.A number of hetero-- and iso--polyanions of molybdenum are re(luci})leto a series of mixed-valeDce compounds containing Mow and Mo t'. f 1 1These species exhibit intervalence transfer bands. This description ofthe electronic structure corresponds to cia88 H syetems in Robinand Day'8 classification of mixed--valence compounds t21. The electrochemical methods can prepare the mixed--valence compounds in which laceetructure of the parent oxidized form is generally retained. [31 In--situepectroelectrochemical studies have many advantages for product identification and for mechanistic studies of transition metal complexes in solution. t.1 Among theme are small electrolysis volumee that yield shortelectrolysis times, rapid time response for the measurement or kineticparameters, and the rapid in--situ generation of reactive species withBtable properties that preclude isolation [51.The cyclic voltammogram indicates that the (TBA).Mo.O.. undergoestwo reductione, which are labeled ac reactions 1--2 and corre6pond tothe electron transfers given in eq. 1-- 2.Mo.O.g-- + e * Mo.O.g--' E./2=--0.690V -----------------------------(1)Mo.O.S-- + e - Mo.O.:-- ac- other products E.,.=--1.650V------(2)展开更多
文摘In the paper, we have studied the mixed-valence isopolyanion by cyclic voltammogram, in-situ UV-Visible-Near-IR and FTIR spectroelectrochemical methods in aprotic medium,such as methylene chloride.A number of hetero-- and iso--polyanions of molybdenum are re(luci})leto a series of mixed-valeDce compounds containing Mow and Mo t'. f 1 1These species exhibit intervalence transfer bands. This description ofthe electronic structure corresponds to cia88 H syetems in Robinand Day'8 classification of mixed--valence compounds t21. The electrochemical methods can prepare the mixed--valence compounds in which laceetructure of the parent oxidized form is generally retained. [31 In--situepectroelectrochemical studies have many advantages for product identification and for mechanistic studies of transition metal complexes in solution. t.1 Among theme are small electrolysis volumee that yield shortelectrolysis times, rapid time response for the measurement or kineticparameters, and the rapid in--situ generation of reactive species withBtable properties that preclude isolation [51.The cyclic voltammogram indicates that the (TBA).Mo.O.. undergoestwo reductione, which are labeled ac reactions 1--2 and corre6pond tothe electron transfers given in eq. 1-- 2.Mo.O.g-- + e * Mo.O.g--' E./2=--0.690V -----------------------------(1)Mo.O.S-- + e - Mo.O.:-- ac- other products E.,.=--1.650V------(2)
