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Influences of Bifunctional PNP-Pincer Ligands on Low Valent Cobalt Complexes Relevant to CO2 Hydrogenation
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-19 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02931
Matthew R. Mills 1 , Charles L. Barnes 1 , Wesley H. Bernskoetter 1
Affiliation  

Pincer ligated coordination complexes bearing bifunctional sites have been at the center of recent developments in reversible hydrogenation catalysis, especially in cases utilizing base metals. The influence of bifunctional ligands on low valent cobalt complexes is detailed here using comparisons between the PNP-pincer ligands MeN[CH2CH2(PR2)]2 and HN[CH2CH2(PR2)]2 (R = iPr, Cy). Comparative catalytic studies of CO2 hydrogenation show that cobalt(I) precatalysts bearing the tertiary amine ligand dramatically outperform those bearing the secondary amine pincer ligand. Despite strong similarities between the precatalyst ground state structure and the redox potentials of the two systems, ligand bifunctionality was found to be detrimental to catalyst productivity. The enhanced stability imparted by the MeN[CH2CH2(PR2)]2 ligand also enabled isolation and characterization of a zero-valent cobalt dicarbonyl species, which was used to study the catalytically active oxidation state of cobalt in CO2 hydrogenation.

中文翻译:

双功能PNP-铁配体对与CO 2加氢有关的低价钴配合物的影响

具有双功能位点的Pincer连接的配位配合物一直是可逆氢化催化的最新进展的中心,特别是在利用贱金属的情况下。本文通过比较PNP-钳位配体MeN [CH 2 CH 2(PR 2)] 2和HN [CH 2 CH 2(PR 2)] 2(R = i Pr,Cy)。CO 2的比较催化研究氢化表明,带有叔胺配体的钴(I)预催化剂大大优于带有仲胺钳形配体的钴(I)预催化剂。尽管在催化剂前基态结构和两个系统的氧化还原电位之间有很强的相似性,但发现配体双功能对催化剂的生产率是有害的。MeN [CH 2 CH 2(PR 2)] 2配体赋予的增强的稳定性也使得能够对零价钴二羰基物质进行分离和表征,该零价钴二羰基物质用于研究CO 2加氢中钴的催化活性氧化态。
更新日期:2018-01-19
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