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Di- and tricobalt Dawson sandwich complexes: Synthesis, spectroscopic characterization, and electrochemical behavior of Na[(NaOH)Co (PWO)] and Na[(NaOH)Co(HO) (PWO)]

Inorganic Chemistry, ISSN: 0020-1669, Vol: 41, Issue: 15, Page: 3811-3819
2002
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Article Description

The reaction of the trivacant Dawson anion α-[PWO] and the divalent cations Co is known to form the tetracobalt sandwich complex [Co(HO)(P WO)] (CoPW). Two new complexes, with different Co/PW stoichiometry, [(NaOH)Co(P WO)] (NaCoPW) and [(NaOH)Co(HO)(P WO)] (NaCoPW), have been synthesized as aqueous-soluble sodium salts, by a slight modification of the reaction conditions. Both compounds were characterized by IR, elemental analysis, and P solution NMR spectroscopy. These species are "lacunary" sandwich complexes, which add Co cations according to NaCoPW + Co → NaCoPW + Na followed by NaCoPW + Co → CoPW + Na. A Li/Na exchange in the cavity was evidenced by 31p dynamic NMR spectroscopy. The electrochemical behaviors of the sandwich complexes [(NaOH)Co(HO)(P WO)] and [(NaOH)Co(P WO)] were investigated in aqueous solutions and compared with that of [Co(HO)(P WO)]. These complexes showed an electrocatalytic effect on nitrite reduction.

Bibliographic Details

Ruhlmann, Laurent; Canny, Jacqueline; Contant, Roland; Thouvenot, René

American Chemical Society (ACS)

Chemistry

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