A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy

Graham E. Ball, Christopher M. Brookes, Alexander J. Cowan, Tamim A. Darwish, Michael W. George, Hajime K. Kawanami, Peter Portius, Jonathan P. Rourke

Research output: Journal PublicationArticlepeer-review

57 Citations (Scopus)

Abstract

The organometallic alkane complexes Re(Cp)(CO)(PF3)(alkane) and Re(Cp)(CO)2(alkane) have been detected after the photolysis of Re(Cp)(CO)2(PF3) in alkane solvent. NMR and time-resolved IR experiments reveal that the species produced by the interaction of n-pentane with [Re(Cp)(CO)(PF3)] are an equilibrium mixture of Re(Cp)(CO)(PF3)(pentane) and Re(Cp)(CO)(PF3)(pentyl)H. The interaction of cyclopentane with [Re(Cp)(CO)(PF3)] most likely results in a similar equilibrium between cyclopentyl hydride and cyclopentane complexes. An increasing proportion of alkane complex is observed on going from n-pentane to cyclopentane to cyclohexane, where only a small amount, if any, of the cyclohexyl hydride form is present. In general, when [Re(Cp)(CO)(PF 3)] reacts with alkanes, the products display a higher degree of oxidative cleavage in comparison with [Re(Cp)(CO)2], which favors alkane complexation without activation. Species with the formula Re(Cp)(CO)(PF3)(alkane) have higher thermal stability and lower reactivity toward CO than the analogous Re(Cp)(CO)2(alkane) complexes.

Original languageEnglish
Pages (from-to)6927-6932
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume104
Issue number17
DOIs
Publication statusPublished - 24 Apr 2007
Externally publishedYes

Keywords

  • Alkane complexes
  • CH activation
  • Multinuclear NMR
  • Photochemistry

ASJC Scopus subject areas

  • General

Fingerprint

Dive into the research topics of 'A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy'. Together they form a unique fingerprint.

Cite this