The transition metal complexes cyclopentadienylrhenium tricarbonyl [CpRe(CO)3, Cp = cyclopentadienyl] and (isopropylcyclopentadienyl)rhenium tricarbonyl [(i-PrCp)Re(CO)3, i-Pr = isopropyl] were photolysed in alkanes at low temperature and the resulting alkane complexes, of the general formula Cp'Re(CO)2(alkane) (Cp' = Cp or (i-PrCp)), were studied using NMR spectroscopy. Characteristic proton chemical shifts (δ) and couplings (3JHH) were observed for alkane complexes of several linear, branched and cyclic alkanes of up to eight carbons. Alkanes with chemically distinct methyl (CH3) and/or methylene (CH2) units were observed alternatively binding through each unit to rhenium. No bound methine unit was observed. Large C-H coupling constants (1JCH) were observed for protons of several bound CH3 and CH2 units, indicating the bound C-H is intact. These species are, thus, alkane sigma (σ) complexes, wherein the alkane has an agostic (M-H-C, 3 centre 2 electron) interaction with the rhenium centre. The CH3 binding mode of (i-PrCp)Re(CO)2(1-pentane) was elucidated; sequential deuteration in the bound CH3 revealed an equilibrium isotope effect (EIE) in the remaining proton/s, confirming that only one C-H has an agostic interaction with rhenium at any instant . NMR parameters δ(1H) (-8.22), δ(13C) ( 42.4) and 1JCH (85 Hz) for the complexed C-H reveal it is unequivocally intact and yet strongly interacting with the rhenium centre, hallmarks for the agostic interaction. Intramolecular exchange was identified between pentane complex isomers Cp'Re(CO)2(1-pentane), Cp'Re(CO)2(2-pentane) and Cp'Re(CO)2(3-pentane). Equilibrium constants were determined, revealing a preference for CH2 binding over CH3. The inequivalent hydrogens found in methylene groups of cyclohexane at low temperature permitted simultaneous observation of axial and equatorial C-H protons of a bound CH2 in CpRe(CO)2(cyclohexane); an EIE, upon deuteration, indicated rapid exchange between complexed C-H bonds in the bound CH2 unit. The rhenium centre was found to prefer complexation of the axial C-H bond, over the equatorial, with K ~2.9. Intermolecular exchange of alkane ligands with free solvent was directly observed, in the competitive complexation of the [CpRe(CO)2] fragment to different alkanes in binary mixtures. The preference cyclohexane > cyclopentane > pentane > isobutane was established and equilibrium constants determined. The kinetics were followed by NMR and modelled, revealing rate constants; decay rates were also determined.
| Identifer | oai:union.ndltd.org:ADTP/242433 |
| Date | January 2008 |
| Creators | Lawes, Douglas John, Chemistry, Faculty of Science, UNSW |
| Publisher | Publisher:University of New South Wales. Chemistry |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | http://unsworks.unsw.edu.au/copyright, http://unsworks.unsw.edu.au/copyright |
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