期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 141, 期 39, 页码 15664-15674出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b07743
关键词
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资金
- NSF [CHE-1800501, CBET-1805022]
- Resnick Sustainability Institute
- NSERC
- Ernest H. Swift Summer Undergraduate Research Fellowship
- Dow Next Generation Education Fund (instrumentation)
- Caltech
The mechanism originally proposed by Fischer and Tropsch for carbon monoxide (CO) hydrogenative catenation involves C-C coupling from a carbide-derived surface methylidene. A single molecular system capable of capturing these complex chemical steps is hitherto unknown. Herein, we demonstrate the sequential addition of proton and hydride to a terminal Mo carbide derived from CO. The resulting anionic methylidene couples with CO (1 atm) at low temperature (-78 degrees C) to release ethenone. Importantly, the synchronized delivery of two reducing equivalents and an electrophile, in the form of a hydride (H- = 2e(-) + H+), promotes alkylidene formation from the carbyne precursor and enables coupling chemistry, under conditions milder than those previously described with strong one-electron reductants and electrophiles. Thermodynamic measurements bracket the hydricity and acidity requirements for promoting methylidene formation from carbide as energetically viable relative to the heterolytic cleavage of H-2. Methylidene formation prior to C-C coupling proves critical for organic product release, as evidenced by direct carbide carbonylation experiments. Spectroscopic studies, a monosilylated model system, and Quantum Mechanics computations provide insight into the mechanistic details of this reaction sequence, which serves as a rare model of the initial stages of the Fischer-Tropsch synthesis.
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