Lengyel Jozef, Levin Nikita, Wensink Frank J, Lushchikova Olga V, Barnett Robert N, Landman Uzi, Heiz Ueli, Bakker Joost M, Tschurl Martin
Lehrstuhl für Physikalische Chemie, Technische Universität München, Lichtenbergstraße 4, 85748, Garching, Germany.
Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525, ED, Nijmegen, The Netherlands.
Angew Chem Int Ed Engl. 2020 Dec 21;59(52):23631-23635. doi: 10.1002/anie.202010794. Epub 2020 Oct 22.
The products of methane dehydrogenation by gas-phase Ta clusters are structurally characterized using infrared multiple photon dissociation (IRMPD) spectroscopy in conjunction with quantum chemical calculations. The obtained spectra of [4Ta,C,2H] reveal a dominance of vibrational bands of a H Ta C carbide dihydride structure over those indicative for a HTa CH carbyne hydride one, as is unambiguously verified by studies employing various methane isotopologues. Because methane dehydrogenation by metal cations M typically leads to the formation of either MCH carbene or HMCH carbyne hydride structures, the observation of a H MC carbide dihydride structure implies that it is imperative to consider this often-neglected class of carbonaceous intermediates in the reaction of metals with hydrocarbons.
利用红外多光子解离（IRMPD）光谱结合量子化学计算，对气相钽团簇催化甲烷脱氢产物进行了结构表征。通过使用各种甲烷同位素异构体的研究明确证实，所获得的[4Ta,C,2H]光谱显示，H-Ta-C碳化物二氢化物结构的振动带比HTa-CH卡宾氢化物结构的振动带占主导地位。由于金属阳离子M催化甲烷脱氢通常会导致形成MCH卡宾或HMCH卡宾氢化物结构，因此观察到H-M-C碳化物二氢化物结构意味着在金属与烃类的反应中，必须考虑这类经常被忽视的含碳中间体。
