CP/MAS NMR and X-ray crystallographic characterization of trans-PdX2(PPh(2)vinyl)(2) (X = Cl, I); UV and Et2O center dot BF3 reaction studies, including the formation of Pd(mu-Cl)(PPh(2)vinyl)(2) (2) BF4 (2)
Hursthouse, M. B., Kelly, D. G., Light, M. E. and Toner, A. J. (2000) CP/MAS NMR and X-ray crystallographic characterization of trans-PdX2(PPh(2)vinyl)(2) (X = Cl, I); UV and Et2O center dot BF3 reaction studies, including the formation of Pd(mu-Cl)(PPh(2)vinyl)(2) (2) BF4 (2). Canadian Journal of Chemistry - Revue Canadienne De Chimie, 78, (8), 1073-1080.
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Description/Abstract
The complexes PdCl2(PPh(2)vinyl)(2) and PdI2(PPh(2)vinyl)(2) have been prepared and crystallographically characterized as their trans square planar isomers. Trans-PdCl2(PPh(2)vinyl)(2) exists in a centrosymmetric structure with a planar PdCl2P2 core whereas trans-PdI2(PPh(2)vinyl)(2) shows no local Pd-centred symmetry and significant distortion of the PdI2P2 core from planarity. Crystallographic data is in accord with the P-31{H-1} CP/MAS NMR spectra of the two complexes, which display a single resonance for the chloro-complex and two resonances for the iodo-complex. UV irradiation of CH2Cl2 solutions of PdCl2(PPh(2)vinyl)(2) followed by re-dissolution in CDCl3 indicates no permanent chemical change. However, post-irradiation CP/MAS P-31{H-1} NMR spectroscopy demonstrates the presence of trans-PdCl2(PPh(2)vinyl)(2) in two solid state structures, plus cis-PdCl2(PPh(2)vinyl)(2). PdI2(PPh(2)vinyl)(2) exists only in its trans form in both solid state and solution. Irradiation results in phosphine displacement and the formation of sym-[PdI2(PPh(2)vinyl)](2) and free phosphine, the latter being characterized as Ph2P(O)vinyl following aerobic oxidation. PdCl2(PPh(2)vinyl)(2) reacts in the presence of Et2O . BF3 to afford [Pd(mu-Cl)(PPh(2)vinyl)(2)](2)[BF4](2) whereas PdI2(PPh(2)vinyl)(2) is recovered in 95% yield, with the remaining material undergoing phosphine abstraction to form sym-[PdI2(PPh(2)vinyl)](2).
| Item Type: | Article |
|---|---|
| Related URLs: | |
| Keywords: | palladium, phosphine, alkene, isomerization, cp/mas palladium(ii) complexes, crystal-structure, phosphine |
| Subjects: | Q Science Q Science > QD Chemistry |
| Divisions: | University Structure - Pre August 2011 > School of Chemistry |
| Item ID: | 19047 |
| Date Deposited: | 17 Jan 2006 |
| Last Modified: | 01 Jun 2011 06:12 |
| Contributors: | Hursthouse, M. B. (Author) Kelly, D. G. (Author) Light, M. E. (Author) Toner, A. J. (Author) |
| Date: | 1 August 2000 |
| Status: | Published |
| URI: | http://eprints.soton.ac.uk/id/eprint/19047 |
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