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A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy
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Ball, Graham E., Brookes, Christopher M., Cowan, Alexander J., Darwish, Tamim A., George, Michael W., Kawanami, Hajime K., Portius, Peter and Rourke, Jonathan P.. (2007) A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy. Proceedings of the National Academy of Sciences of the United States of America, Vol.104 (No.17). pp. 6927-6932. ISSN 0027-8424
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Official URL: http://dx.doi.org/10.1073/pnas.0610212104
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)(PF3)] 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.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science |
| Divisions: | Faculty of Science > Chemistry |
| Journal or Publication Title: | Proceedings of the National Academy of Sciences of the United States of America |
| Publisher: | National Academy of Sciences |
| ISSN: | 0027-8424 |
| Date: | 24 April 2007 |
| Volume: | Vol.104 |
| Number: | No.17 |
| Number of Pages: | 6 |
| Page Range: | pp. 6927-6932 |
| Identification Number: | 10.1073/pnas.0610212104 |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Restricted or Subscription Access |
| URI: | http://wrap.warwick.ac.uk/id/eprint/32043 |
Data sourced from Thomson Reuters' Web of Knowledge
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