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, 78 (8), 1073-1080.

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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