Preparative and structural studies on the carbonyl cyanides of iron, manganese, and ruthenium: Fundamentals relevant to the hydrogenases

Stephen M. Contakes, Sodio C.N. Hsu, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticle

Abstract

The reaction of cyanide, carbon monoxide, and ferrous derivatives led to the isolation of three products, trans- and cis-[Fe(CN)4(CO)2]2- and [Fe(CN)5(CO)]3-, the first two of which were characterized by single-crystal X-ray diffraction. The new compounds show self-consistent IR, 13C NMR, and mass spectroscopic properties. The reaction of trans-[Fe(CN)4(CO)2]2- with Et4NCN gives [Fe(CN)5(CO)]3- via a first-order (dissociative) pathway. The corresponding cyanation of cis-[Fe(CN)4(CO)2]2-, which is a minor product of the Fe(II)/CN-/CO reaction, does not proceed at measurable rates. Methylation of [Fe(CN)5(CO)]3- gave exclusively cis-[Fe(CN)4(CNMe)(CO)]2-, demonstrating the enhanced nucleophilicity of CN- trans to CN- vs CN- trans to CO. Methylation has an electronic effect similar to that of protonation as determined electrochemically. We also characterized [M(CN)3(CO)3]n- for Ru (n = 1) and Mn (n = 2) derivatives. The Ru complex, which is new, was prepared by cyanation of a [RuCl2(C0)3]2 solution.

Original languageEnglish (US)
Pages (from-to)1670-1678
Number of pages9
JournalInorganic Chemistry
Volume41
Issue number6
DOIs
StatePublished - Mar 25 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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