C-Cl bond activation and catalytic hydrodechlorination of hexachlorobenzene by cobalt and nickel complexes with sodium formate as a reducing agent

Junye Li; Xiaoyan Li; Lin WangQingping HuHongjian Sun

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C-Cl bond activation and catalytic hydrodechlorination of hexachlorobenzene by cobalt and nickel complexes with sodium formate as a reducing agent

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A benzyne cobalt complex, Co(η2-C6Cl4)(PMe3)3 (2), was generated from the reaction of hexachlorobenzene with 2 equiv. of Co(PMe_3)_4 through selective activation of two C-Cl bonds of hexachlorobenzene. Meanwhile, the byproduct CoCl_2(PMe_3)_3 was also confirmed by IR spectra. The cobalt(II) complex, CoCl-(C_6C_(l5))(PMe_3)_3 (1), as an intermediate in the formation of aryne complex 2, was also isolated by the reaction of hexachlorobenzene with the stoichiometric amount of Co(PMe_3)_4. Complex 2 could be obtained by the reaction of 1 with Co(PMe_3)_4. Under similar reaction conditions, the reaction of Ni(PMe_3)_4 with hexachlorobenzene afforded only a mono-(C-Cl) bond activation nickel(II) complex, NiCl(C_6H_5)(PMe_3)_2(5). The expected benzyne nickel complex was not formed. The structures of complexes 2 and 5 were determined by X-ray single crystal diffraction. Successful selective hydrodechlorinations of hexachlorobenzene were studied and in the presence of Co(PMe_3)_4 or Ni(PMe_3)_4 as catalysts and sodium formate as a reducing agent pentachlorobenzene and 1,2,4,5-tetrachlorobenzene were obtained. The catalytic hydrodechlorination mechanism is proposed and discussed.

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《Dalton transactions: An international journal of inorganic chemistry》 |2014年第18期|6660-6666|共7页
作者
Junye Li; Xiaoyan Li; Lin WangQingping HuHongjian Sun;
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作者单位

School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250199 Jinan, PR China.;

School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27, 250199 Jinan, PR China;

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正文语种英语
中图分类化学;无机化学;
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activation; catalytic; hydrodechlorination;

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C-Cl bond activation and catalytic hydrodechlorination of hexachlorobenzene by cobalt and nickel complexes with sodium formate as a reducing agent

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