三甲基膦支持的硒配位钴氢配合物的合成和性质

Synthesis and Properties of a Se-Coordinated Hydrido Cobalt(Ⅲ) Complex Supported by Trimethylphosphine

通过4-甲氧基苯硒酚和2-甲基苯硒酚分别与Co(PMe_3)_4反应生成了单核Co(Ⅱ)配合物[Co(4-MeOC_6H_4Se)_2-(PMe_3)_3](1)和双核Co(Ⅰ)配合物[Co(PMe_3)_2(SeC_6H_4-2-Me)]_2(2).配合物2与CO作用形成了配合物[Co(PMe_3)_2(CO)_2(SeC_6H_4-2-Me)](3).而苯硒酚与Co(PMe_3)_4反应制备了硒配位的钴氢配合物[mer-Co(H)(SePh)_2(PMe_3)_3](4)和双核Co(I)配合物[Co(PMe_3)_2(SePh)]_2(5).初步研究表明4对于醛和酮的硅氢化反应有一定的催化效果.配合物1,3和4的分子结构通过X射线衍射进行了证实.

A mononuclear cobalt（Ⅱ） complex [Co（4-MeOC_6H_4Se）_2-（PMe_3）_3]（1） and a dinuclear cobalt diphenylselenolato complex [Co（PMe_3）_2（SeC_6H_4-2-Me）]_2（2） were obtained from the reaction of 4-methoxyselenophenol and 2-methylselenophenol with Co（PMe_3）_4, respectively. The dicarbonyl cobalt（Ⅰ） complex [Co（PMe_3）_2（CO）_2（SeC_6H_4-2-Me）]（3） was formed through the reaction of complex 2 with carbon monoxide. A novel selenophenolato hydridocobalt（III） complex [mer-Co（H）（SePh）_2（PMe_3）_3]（4） and a dinuclear cobalt diphenylselenolato complex [Co（PMe_3）_2（Se Ph）]_2（5） were synthesized by the reaction of selenophenol with Co（PMe_3）_4. It was found that complex 4 could catalyze the hydrosilylation of aldehydes and ketones. The molecular structures of 1, 3 and 4 were determined by X-ray diffraction.