Alberico Elisabetta, Leischner Thomas, Junge Henrik, Kammer Anja, Sang Rui, Seifert Jenny, Baumann Wolfgang, Spannenberg Anke, Junge Kathrin, Beller Matthias
Leibniz-Institut für Katalyse e. V. Albert-Einstein Straße 29a 18059 Rostock Germany
Istituto di Chimica Biomolecolare, Consiglio Nazionale delle Ricerche tr. La Crucca 3 07100 Sassari Italy
Chem Sci. 2021 Aug 31;12(39):13101-13119. doi: 10.1039/d1sc04181a. eCollection 2021 Oct 13.
Molybdenum(0) complexes with aliphatic aminophosphine pincer ligands have been prepared which are competent for the disproportionation of formic acid, thus representing the first example so far reported of non-noble metal species to catalytically promote such transformation. In general, formic acid disproportionation allows for an alternative access to methyl formate and methanol from renewable resources. MeOH selectivity up to 30% with a TON of 57 could be achieved while operating at atmospheric pressure. Selectivity (37%) and catalyst performance (TON = 69) could be further enhanced when the reaction was performed under hydrogen pressure (60 bars). A plausible mechanism based on experimental evidence is proposed.
已制备出与脂肪族氨基膦钳形配体形成的钼(0)配合物，该配合物能够使甲酸发生歧化反应，因此代表了迄今为止报道的首例能够催化促进这种转化的非贵金属物种。一般来说，甲酸歧化反应为从可再生资源制备甲酸甲酯和甲醇提供了一种替代途径。在大气压下操作时，甲醇选择性可达30%，转化数为57。当反应在氢气压力（60巴）下进行时，选择性（37%）和催化剂性能（转化数=69）可进一步提高。基于实验证据提出了一种合理的机理。
