Synthesis and X-ray crystal structures of organotri(2-furyl)phosphonium salts: effects of 2-furyl substituents at phosphorus on intramolecular nitrogen to phosphorus hypervalent coordinative interactions
Allen, David W., Coles, Simon J., Light, Mark E. and Hursthouse, Michael B. (2004) Synthesis and X-ray crystal structures of organotri(2-furyl)phosphonium salts: effects of 2-furyl substituents at phosphorus on intramolecular nitrogen to phosphorus hypervalent coordinative interactions. Inorganica Chimica Acta, 357, (5), 1558-1564. (doi: 10.1016/j.ica.2003.12.001).
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Description/Abstract
The synthesis of tri(2-fur)(8-quinolylmethyl)phosphonium bromide and 2-[2-tri(2-furyl)phosphoniophenyl]benzimidazole perchlorate is described, the latter involving a nickel(II)-catalysed displacement of bromine from 2-(2-bromophenyl)benzimidazole by tri(2-furyl)phosphine. X-ray structural Studies of the phosphoniobenzimidazole salt reveals the existence of a significant hypervalent coordinative interaction between heterocyclic nitrogen and the phosphonium centre, which also appears to be retained in solution, the P-31 NMR spectrum showing a significantly shielded phosphorus atom, delta(31)P = ca. -40 ppm in CDCl3. The structure of the phosphoniophenylbenzimidazole cation reveals major distortion of bond angles about phosphorus away from the idealised tetrahedral angles expected for a tetraarylphosphonium salt, in the range 102-116degrees. Three of the angles are reduced below the tetrahedral angle and three are increased, the structure about phosphorus approaching that of a trigonal bipyramid, in which the heterocyclic imino nitrogen forms part of a five-membered ring spanning apical-equatorial positions. The apical axis of the trigonal bipyramid is formed by this nitrogen atom and one of the 2-furyl groups, the apical axial bond angle (N2-P-Cl4) being an average of 178degrees. The remaining 2-furyl groups occupy equatorial positions, along with the phenyl ring. Significantly, the nitrogen-phosphorus distance is an average of 2.67 Angstrom (for two independent molecules in the unit cell), being the shortest observed in structures of this type, a consequence of the electron-withdrawing properties of the 2-furyl substituents at phosphorus. The structure also shows edge to face associations of 2-furyl substituents of one cation with the phenyl ring of the benzimidazole unit of another cation. The perchlorate anion is hydrogen-bonded to the nitrogen bearing the hydrogen atom in the benzimidazole ring system. In contrast, the N-P interaction in the quinolylmethylphosphonium salt is much less developed. with an N-P distance of 3.511 Angstrom, although there is considerable deformation of bond angles at phosphorus. The crystal structure is dominated by the existence of hydrogen-bonded interactions between the cation, anion and a molecule of water, and by face to face interactions between cations. Both salts undergo loss of a 2-furyl group on treatment with hydroxide ion.
| Item Type: | Article |
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| Related URLs: | |
| Keywords: | crystal structures, heteroaryl substituents, hypercoordination, hypervalency, p-31 nmro donor action, alkaline-hydrolysis, heteroarylphosphorus compounds,arylphosphonium salts, catalyzed formation, chemistry, silicon, phosphines, betaines, cations |
| Subjects: | Q Science > QD Chemistry |
| Divisions: | University Structure - Pre August 2011 > School of Chemistry |
| Item ID: | 20116 |
| Date Deposited: | 23 Feb 2006 |
| Last Modified: | 01 Jun 2011 03:57 |
| Contributors: | Allen, David W. (Author) Coles, Simon J. (Author) Light, Mark E. (Author) Hursthouse, Michael B. (Author) |
| Date: | 25 March 2004 |
| Status: | Published |
| URI: | http://eprints.soton.ac.uk/id/eprint/20116 |
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