3 years ago

CO-Reduction Chemistry: Reaction of a CO-Derived Formylhydridoborate with Carbon Monoxide, with Carbon Dioxide, and with Dihydrogen

CO-Reduction Chemistry: Reaction of a CO-Derived Formylhydridoborate with Carbon Monoxide, with Carbon Dioxide, and with Dihydrogen
Stefan Grimme, Melanie Siedow, Hellmut Eckert, Thomas Wiegand, Zhongbao Jian, Markus Bursch, Gerald Kehr, Constantin G. Daniliuc, Gerhard Erker, Birgit Wibbeling
Treatment of the bulky metallocene hydride Cp*2Zr(H)OMes (Cp* = pentamethylcyclopentadienyl, Mes = mesityl) with Piers’ borane [HB(C6F5)2] and carbon monoxide (CO) gave the formylhydridoborate complex [Zr]–O═CH–BH(C6F5)2 ([Zr] = Cp*2Zr–OMes). From the dynamic NMR behavior, its endergonic equilibration with the [Zr]–O–CH2–B(C6F5)2 isomer was deduced, which showed typical reactions of an oxygen/boron frustrated Lewis pair. It was trapped with CO to give an O–[Zr] bonded borata-β-lactone. Trapping with carbon dioxide (CO2) gave the respective O–[Zr] bonded cyclic boratacarbonate product. These reaction pathways were analyzed by density functional theory calculation. The formylhydridoborate complex was further reduced by dihydrogen via two steps; it reacted rapidly with H2 to give Cp*2Zr(OH)OMes and H3C–B(C6F5)2, which then slowly reacted further with H2 to eventually give [Zr]–O(H)–B(H)(C6F5)2 and methane (CH4). Most complexes were characterized by X-ray diffraction.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02548

DOI: 10.1021/jacs.7b02548

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