The first precise molecular structure of a monomeric transition metal cyanide, copper(I) cyanide

Douglas B. Grotjahn, M. A. Brewster, Lucy M. Ziurys

Research output: Contribution to journalArticle

68 Scopus citations

Abstract

Copper(I) cyanide is an important reagent in organic, organometallic, and supramolecular chemistry because of both the copper center and the versatile cyanide ligand. Solid-phase CuCN and many of its derivatives show oligomeric or polymeric structures, a trait shared by other metal cyanides. Often, it is difficult to specify the orientation of the cyano ligand in an X-ray structure. Here the first preparation and precise structure of a monomeric transition metal cyanide is reported. Gas-phase reaction between copper vapor and cyanogen (NCCN) clearly gives CuCN (not CuNC). The precise structure of CuCN so produced is determined by millimeter/submillimeter-wave spectroscopy. Because of the highly efficient synthesis and the presence of significant amounts of two copper isotopes, such strong signals were seen that natural-abundance materials allowed observation of transitions for the four isotopomers 63Cu12C14N, 65Cu12C14N, 63Cu13C14N, and 63Cu12C15N and the determination of ro, r, and rm(2)structures. All data unequivocally show a linear geometry and that the carbon of cyanide is bound to copper with a Cu-C distance of 1.82962(4) Å in the structure, which is likely to be closest to the equilibrium geometry.

Original languageEnglish (US)
Pages (from-to)5895-5901
Number of pages7
JournalJournal of the American Chemical Society
Volume124
Issue number20
DOIs
StatePublished - May 22 2002

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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