New low-spin Co(II) complexes with novel tripodal 1,1,1-tris(dimethylphosphinomethyl)ethane ligand: electron transfer kinetics and spectroscopic characterization of Co(II)P6 and Co(II)P3S3 ions in aqueous solution

Abstract

Substitution-inert Co(II) complexes with tripodal 1,1,1-tris(dimethylphosphinomethyl)ethane were produced in aqueous solution by the controlled-potential electrolysis. EPR studies indicated that the Co(II)P6 and Co(II)P3S3 species are in the low-spin t62ge1g state. The analyses of the absorption spectra of the Co(II) species in solution indicated significant Jahn–Teller distortion in Co(II)P6 and Co(II)P3S3 ions as expected for the low-spin d7 electronic configuration, while less distortion was observed for the Co(II)S6 ion. Kinetic studies of the redox reactions involving these Co(III/II) species confirmed that the electron self-exchange reactions for the Co(III/II)P6 and Co(III/II)P3S3 couples are relatively fast (kex ~ 1 × 104 dm3 mol–1 s–1), which is consistent with the results for other low-spin – low-spin Co(III/II) couples. It was concluded that the nephelauxetic effect of the P-donor atom stabilizes the low-spin state in Co(II), and that the rather rapid electron exchange rates for these Co(III/II) couples were explained by the lack of the spin reorganization process required for the ordinary low-spin – high-spin Co(III/II) couples.Key words: cobalt(III/II), spin state, EPR study, kinetics, electron transfer.