Electrochemical Synthesis and Structure of Sn[Co(CO)4]4 and Its Use as a Stable Precursor of [Co(CO)4]- for the Catalysis of Hydrolysis of Propylene Carbonate

Armando Cabrera, Henri Samain, André Mortreux, Francis Petit, Alan J. Welch

Research output: Contribution to journalArticle

Abstract

The complex Sn[Co(CO)4]4 (I) has been prepared in high yield by the controlled potential electrolysis of Co2(CO)8 in the presence of a tin anode. The major advantage afforded by this electrochemical synthesis is to produce I quickly and cleanly. Results of an X-ray diffraction study on I are reported. We have established that I and Co2(CO)8 are very active catalysts for the hydrolysis of cyclic organic carbonates. The 100% selectivity in monoglycol is in marked contrast to other catalytic systems that require an excess of water to inhibit production of polyglycols. Studies, under various CO pressures, of the catalytic activities of Co2(CO)8 and I during the hydrolysis of propylene carbonate have led us to suggest that (i) [Co(CO)4]- is the active moiety, (ii) I can eliminate Co2(CO)8, and (iii) I is more stable than Co2(CO)8 at low CO pressures. Isotopic analysis of the remaining substrate and products after the hydrolysis of propylene carbonate by H218O show that (iv) the attack of water occurs at the carbonyl site of the carbonate and (v) it is likely that hydration is activated by [Co(CO)4]-.

Original languageEnglish
Pages (from-to)959-964
Number of pages6
JournalOrganometallics
Volume9
Issue number4
DOIs
Publication statusPublished - 1 Apr 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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