Synthesis and Catalytic Reactivity of Cobalt Pincer Nitrosyl Hydride Complexes,Organometallics

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Synthesis and Catalytic Reactivity of Cobalt Pincer Nitrosyl Hydride Complexes
Organometallics ( IF 2.5 ) Pub Date : 2021-01-05 , DOI: 10.1021/acs.organomet.0c00755
Jan Pecak ₁ , Sarah Fleissner ₁ , Luis F. Veiros ₂ , Ernst Pittenauer ₃ , Berthold Stöger ₄ , Karl Kirchner ₁

Affiliation

The synthesis, characterization, and catalytic activity of low-spin {CoNO}⁸ pincer complexes of the type [Co(PCP)(NO)(H)] are described. These compounds are obtained either by reacting [Co(PCP)(κ²-BH₄)] with NO and Et₃N or, alternatively, by reacting [Co(PCP)(NO)]⁺ with boranes, such as NH₃·BH₃ in solution. The five-coordinate, diamagnetic Co(III) complex [Co(PCP^NMe-iPr)(NO)(H)] was found to be the active species in the hydroboration of alkenes with anti-Markovnikov selectivity. A range of aromatic and aliphatic alkenes were efficiently converted with pinacolborane (HBpin) under mild conditions in good to excellent yield. Mechanistic insight into the catalytic reaction is provided by means of isotope labeling, NMR spectroscopy, and APCI/ESI-MS as well as DFT calculations.

中文翻译：

钴夹钳亚硝酰氢化物配合物的合成及催化活性

描述了类型[Co（PCP）（NO）（H）]的低旋{CoNO} ⁸钳形配合物的合成，表征和催化活性。通过以下反应获得任一这些化合物[CO（PCP）（κ ² -BH ₄）]与NO和Et ₃ N或，可选地，通过使[CO（PCP）（NO）] ⁺与硼烷，如NH ₃ ·溶液中的BH ₃。五坐标抗磁性Co（III）络合物[Co（PCP ^NMe - i发现Pr）（NO）（H）]是具有反马尔科夫尼科夫选择性的烯烃加氢硼化反应中的活性物质。频哪醇硼烷（HBpin）在温和的条件下以高至优异的收率有效地转化了多种芳族和脂族烯烃。借助同位素标记，NMR光谱，APCI / ESI-MS以及DFT计算，可以对催化反应进行深入的研究。

更新日期：2021-01-25

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