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

Ball, Graham E., Brookes, Christopher M., Cowan, Alexander J., Darwish, Tamim A., George, Michael W., Kawanami, Hajime K., Portius, Peter and Rourke, Jonathan P. ORCID: https://orcid.org/0000-0002-8961-1021 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 104 (17) , pp. 6927-6932. 10.1073/pnas.0610212104

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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:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
ISSN:	0027-8424
Last Modified:	17 Mar 2023 15:42
URI:	https://orca.cardiff.ac.uk/id/eprint/157789

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