Browse by author
Lookup NU author(s): Professor William Clegg, Professor Todd Marder
Full text for this publication is not currently held within this repository. Alternative links are provided below where available.
In order to evaluate the potential for side reactions when using B-chlorocatechol borane (ClBcat) in stoichiometric or catalytic transformations involving metal phosphine complexes, we examined the interaction between ClBcat and a series of PR3 compounds. Reactions of ClBcat with the basic phosphines PMe3, PEt3, PMe2Ph and PBu3t, in exactly 1∶1 stoichiometry, all afforded crystalline adducts of the form R3P . ClBcat, which have been characterised spectroscopically. All display broad singlets at room temperature in both B-11{H-1} and P-31{H-1} NMR spectra with no B-P coupling observed. The low temperature B-11{H-1} and P-31{H-1} NMR spectra, however, do show B-P coupling, suggesting rapid dissociation at room temperature. The compounds ClBcat, BrBcat, and the adducts between ClBcat and PMe3, PEt3 and PBu3t have been characterised by single crystal X-ray diffraction. In ClBcat and BrBcat, the halogen contributes little pi -bonding to boron as the B-O bond lengths are identical in both compounds. The reaction of ClBcat with a small excess of PCy3 yielded Cy3P . ClBcat, which has also been characterised by single crystal X-ray diffraction and shows considerable distortion. The reaction between ClBcat and the less basic phosphines PPh3 and PPh2Me yielded only the redistribution products R3P . BCl3 and B(2)cat(3). In fact, reaction of all of the phosphines with an excess of ClBcat gave only redistribution products, although there was evidence for an intermediate in the B-11{H-1} NMR spectra, with PMe3 and PEt3. The isolated R3P . ClBcat adducts proved unstable, even at low temperature in the solid state, eventually leading to R3P . BCl3 and B(2)cat(3). Reaction of ClBcat with NEt3 afforded Et3N . ClBcat, which was characterised spectroscopically and by single crystal X-ray diffraction. This adduct is stable both in solution and in the solid state.
Author(s): Coapes RB, Souza FES, Fox MA, Batsanov AS, Goeta AE, Yufit DS, Leech MA, Howard JAK, Scott AJ, Clegg W, Marder TB
Publication type: Article
Publication status: Published
Journal: Journal of the Chemical Society: Dalton Transactions
Year: 2001
Issue: 8
Pages: 1201-1209
ISSN (print): 1472-7773
ISSN (electronic): 1364-5447
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b010025k
DOI: 10.1039/b010025k
Altmetrics provided by Altmetric
