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Cyclic voltammetric studies of clusters(C_6H_5-C_2C_6 H_4-R-p)Co_2(CO)_(6-n) L_n[n=0,2;L=PPh_3,P(OEt)_3] and(RCH_2C)_2Co_2(CO_4)(PPh_3)_2 on Pt electrode are described. The primaryreduction(0/-1)and oxidation (+1/0) steps are considered as a mono-electron process for allclusters. For the clusters (C_6H_5C_2C_6H_4-R-P)Co_2(CO)_6, a good linear relation between reduction poten-tial EF_p~(red) and Hammett constant σp of R in the clusters is found. For the clusters(RC_2R′)Co_2(CO)_4L_2,their radical anions are extremely unstable at room temperature and fragment into a series of mono-nuclear species, one of which is(RC-3R′)Co(CO)_2PPh_3. The reaction of radical anions of (RC_2R’)-Co_2(CO)_(6-n) (PPh_3)_n(n=0,2) with PPh_3 also produces mononuclear species (RC_2R’)Co(CO)_2PPh_3which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox pro-perties of clusters is discussed.
Cyclic voltammetric studies of clusters (C_6H_5-C_2C_6H_4-Rp) Co_2 (CO) _ (6-n) L_n [n = 0,2; L = PPh_3, P (OEt) _3] and (RCH_2C) _2Co_2 (CO_4) The primary reduction (0 / -1) and oxidation (+1/0) steps are considered as a mono-electron process for all clusters. For the clusters (C_6H_5C_2C_6H_4-RP) Co_2 (CO) _6 , a good linear relation between reduction poten- tial EF_p ~ red and Hammett constant σp of R in the clusters is found. For the clusters (RC_2R ’) Co_2 (CO) _4L_2, their radical anions are extremely unstable at room temperature and The fragment of a series of mono-nuclear species, one of which is (RC-3R ’) Co (CO) _2PPh_3. The reaction of radical anions of (RC_2R’) - Co_2 (CO) _ (6-n) _n (n = 0,2) with PPh_3 also produces mononuclear species (RC_2R ’) Co (CO) _2PPh_3which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox pro-perties of clusters is discussed.