Redox properties of (RC2R')Co2(CO)6-nLn and reactivity of (RC2R')Co2(CO)6-nLn towards PPh3[LPPh3, P(OEt)3] |
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Authors: | Qing-Jin Meng Shou-Heng Sun Xiao-Zeng You |
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Abstract: | Cyclic voltammetric studies of clusters (C5H5-C2C6 H4-R-p)Co2(CO)6-n Lnn=0,2; L=PPh3, P(OEt)3] and (RCH2C)2Co2(CO4) (PPh3)2 on Pt electrode are described. The primary reduction (0 / ?1) and oxidation (+ 1 / 0) steps are considered as a mono-electron process for all clusters. For the clusters (C5H5C2C6H4-R-p)Co2(CO)6, a good linear relation between reduction potential Epred and Hammett constant σp of R in the clusters is found. For the clusters (RC2R')Co2(CO)4L2, their radical anions are extremely unstable at room temperature and fragment into a series of mononuclear species, one of which is (RC2R')Co(CO)2PPh3. The reaction of radical anions of (RC2R')Co2(CO)6–n (PPh3)n(n=0,2) with PPh3 also produces mononuclear species (RC2R')Co(CO)2PPh3 which has been detected by means of cyclic voltammetry and ESR. The influence of R on redox properties of clusters is discussed. |
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