The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds?

Carlito B Lebrilla, Thomas Drewello, Helmut Schwarz

Research output: Contribution to journalArticle

30 Scopus citations

Abstract

Experimental evidence is presented that RCN/M+ complexes (M = Co, Ni) exhibit practically identical reactivities upon collisional activation in the gas phase, while the analogous RCN/Fe+ systems are distinct. Insertion of the (complexed) transition metal ion M+ into internal CH bonds of linear alkyl nitriles commences for the RCN/Fe+ system with C(8) while, for the RCN/Co+ and RCN/Ni+ species, a trajectory is operative by which insertion occurs already at C(7). This behaviour can be explained by the different bonding situation of the RCN/Fe+ versus RCN/M+ (M = Co, Ni) systems. In the former, the deviation from the linear C-C-N-Fe+ alignment is less pronounced than in the C-C-N-M+ system (M = Co, Ni) with the consequence that CH bonds of the methylene chain closer to the functional group add oxidatively to the metal ion for M = Co, Ni. Some analogies with the recently described metal-silylene system are discussed.

Original languageEnglish (US)
Pages (from-to)287-294
Number of pages8
JournalInternational Journal of Mass Spectrometry and Ion Processes
Volume79
Issue number3
DOIs
StatePublished - Nov 25 1987
Externally publishedYes

ASJC Scopus subject areas

  • Spectroscopy

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