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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)

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)
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)
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).
palladium, phosphine, alkene, isomerization, cp/mas palladium(ii) complexes, crystal-structure
1073-1080
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kelly, D. G.
c64371f1-a702-439f-9c18-50a5b25ba64c
Light, M. E.
5f2f6119-008d-4681-8ea0-e32559c94ddd
Toner, A. J.
3a1b0c3b-73bc-400b-a681-babb3838e2f6
Hursthouse, M. B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kelly, D. G.
c64371f1-a702-439f-9c18-50a5b25ba64c
Light, M. E.
5f2f6119-008d-4681-8ea0-e32559c94ddd
Toner, A. J.
3a1b0c3b-73bc-400b-a681-babb3838e2f6

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, 78 (8), 1073-1080.

Record type: Article

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).

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More information

Published date: 1 August 2000
Keywords: palladium, phosphine, alkene, isomerization, cp/mas palladium(ii) complexes, crystal-structure

Identifiers

Local EPrints ID: 19047
URI: http://eprints.soton.ac.uk/id/eprint/19047
PURE UUID: 09cc8bfc-27e0-47da-bdc4-adfd34142090

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Date deposited: 17 Jan 2006
Last modified: 11 Dec 2021 14:21

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Contributors

Author: D. G. Kelly
Author: M. E. Light
Author: A. J. Toner

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