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作为氢化催化剂的烯烃金属盐。

Alkene Metalates as Hydrogenation Catalysts.

作者信息

Büschelberger Philipp, Gärtner Dominik, Reyes-Rodriguez Efrain, Kreyenschmidt Friedrich, Koszinowski Konrad, Jacobi von Wangelin Axel, Wolf Robert

机构信息

Institute of Inorganic Chemistry, University of Regensburg, Universitätsstr. 31, 93040, Regensburg, Germany.

Institute of Organic Chemistry, University of Regensburg, 93040, Regensburg, Germany.

出版信息

Chemistry. 2017 Mar 2;23(13):3139-3151. doi: 10.1002/chem.201605222. Epub 2017 Feb 6.

DOI:10.1002/chem.201605222
PMID:28026060
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5861671/
Abstract

First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo- and heteroleptic arene/alkene metalates(1-) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(η -cod)(η -styrene) ] (5) and [K([18]crown-6)][Co(η -dct)(η -cod)] (6), and the homoleptic complex [K(thf) ][Co(η -dct) ] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1-) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H , r.t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral π-ligand exchange with the substrates followed by H activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).

摘要

第一排过渡金属配合物作为氢化及相关还原反应的催化剂具有巨大潜力。均配和异配芳烃/烯烃金属酸盐（1-）（M = Co、Fe）是一类结构独特的催化剂，在烯烃和炔烃的氢化反应中具有良好的活性。本文报道了异配钴酸盐[K([18]冠醚-6)][Co(η -环辛二烯)(η -苯乙烯) ]（5）和[K([18]冠醚-6)][Co(η -二苯并[a,e]环辛四烯)(η -环辛二烯)]（6）以及均配配合物[K(四氢呋喃) ][Co(η -二苯并[a,e]环辛四烯) ]（7；dct = 二苯并[a,e]环辛四烯，cod = 1,5 - 环辛二烯）的首次合成。为作比较，按照文献方法合成了两种环戊二烯基铁酸盐（1-）。分离得到并经充分表征的单阴离子配合物在温和条件下（2 bar H ，室温，四氢呋喃）是烯烃氢化反应的有效预催化剂。通过核磁共振光谱、电喷雾电离质谱和中毒实验进行的机理研究证明了均相机理的运行，该机理由与底物进行的简便氧化还原中性π-配体交换引发，随后是氢活化。所研究的预催化剂的底物范围也扩展到了极性底物（酮和亚胺）。

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