Journal of Organometallic Chemistry p. 63 - 70 (2000)
Update date:2022-08-11
Topics:
King, Charles M.
Bruce King
Bhattacharyya, Nripendra K.
Gary Newton
Soluble homogeneous organophosphorus - nickel complexes have been used to detoxify polychlorinated biphenyls (PCBs) by catalyzed hydrodechlorination using NaBH2(OCH2CH2OCH3)2 as the hydrogen source. The reactions appear to proceed by NiL3 oxidative addition into C-Cl bonds followed by hydrogenolysis of the metal-carbon bond. In model experiments with decachlorobiphenyl, the cone angle of the organophosphorus ligand L was shown to be a key factor controlling the magnitude and position of chlorine displacement. Hence, ligands leading to para displacement (e.g. (o-MeC6H4O)3P), meta - para displacement (e.g. (EtO)3P and (PhO)3P), and ortho - meta - para displacement (e.g. Me3P and Et3P) were found. Significantly, the highly toxic, coplanar dioxin precursor 3,3′,4,4′-tetrachlorobiphenyl, a meta - para chlorine-substituted congener, was dechlorinated quantitatively with the Et3P catalyst system. Evidence for the presence of organonickel intermediates in the reaction mixtures was obtained by mass spectroscopic and X-ray diffraction studies. Of particular interest is the isolation of square planar complexes p-C6Cl5C6Cl4Ni(PEt3) 2Cl from the reaction of decachlorobiphenyl with NaBH2(OCH2CH2OCH3)2 - (Et3P)2NiCl2 as the catalyst precursor and m-C6Cl5C6Cl4Ni(PEt3) 2Cl from decachlorobiphenyl - Ni(1,5-C8H12)2 - PEt3 at room temperature. All are oxidative addition intermediates and precursors for decachlorobiphenyl hydrodechlorination.
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