Electron transfer between metal complexes, table

Table 9.2 Test of the Marcus cross-relation Comparison of observed rate constants for electron-transfer reactions between metal complex ions with values calculated from rate constants observed for the related electron-exchange reactions (Equation (9.41)). Data from R.A. Marcus and N. Sutin, Ref. [13]...

The catalytic cycles for reduction of alkyl and atyl halides using Ni(o), Co(i) or Pd(o) species are interrupted by added carbon dioxide and reaction between the first formed carbon-metal bond and carbon dioxide yields an alkyl or aryl car-boxylate. These catalyses reactions have the advantage of occuriiig at lower cathode potentials than the direct processes summarised in Table 4.14. Mechanisms for the Ni(o) [240] and Pd(o) [241] catalysed processes have been established. Carbon dioxide inserts into the carbon-metal bond in an intermediate. Once the carboxy-late-metal species is formed, a further electron transfer step liberates the carboxy-late ion reforming the metallic complex catalyst. 

The coordination atmosphere of the metal ion in solution can also be expected to affect the reaction rate. Microanalytical results indicate that the active catalysts in cobalt and nickel systems could well be metal thiolic species produced in situ. However, these complexes are appreciably more soluble in the, alkaline solutions than are metal hydroxides (see, for example, the analysis results reported in Table IV), and it is not possible on the present evidence to differentiate between catalysis as a result of increased solubility (comparing metal hydroxides and metal thiolic complexes), and catalysis as a result of differences in the allowed ease of electron transfer. It is apparent, however, that most of the metals investigated (Table I) are poor catalysts because they form only the insoluble hydroxide complexes. 

Polyvinyl Chloride. Biswas and Moitra [102] observed substantial increase in conductivity for metal modified PVC (Fig. 29). Table 1 presents the electrical conductivity data of the PVC-DMG-M(II) complexes. Interestingly, conductivities appreciably increase relative to PVC in the order PVC < PVC-DMG-Cu(II) < PVC-DMG-Ni(II) < PVC-DMG-Co(II). The enhancement in the conductivity is readily ascribable to the varying extents of charge transfer between the 3d metal ion centers and the electron-rich heteroatoms in DMG. Apparently, ease of such charge transfer will depend upon the availability of M vacant orbitals which follows the order Co2 + (3d1) > Ni2+(3d8) > Cu2 + (3d9). 

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