2875-94-7Relevant articles and documents
FTIR matrix-isolation study of the reaction products of vanadium atoms with propene: Observation of allylvanadium hydride as a precursor to sacrificial hydrogenation of propene
Thompson, Matthew G. K.,Walker, Stephen W. C.,Parnis, J. Mark
, p. 7317 - 7323 (2011)
Vanadium atoms have been reacted with different partial pressures of propene in Ar under matrix-isolation conditions, and the products have been observed using Fourier transform infrared (FTIR) spectroscopy. Under dilute propene in Ar conditions, new features are observed in the IR spectra corresponding to a C-H insertion product, identified here as H-V-(η3-allyl). Use of d3-propene (CD 3-CH=CH2) demonstrates that the initial V-atom insertion occurs at the methyl group of the propene molecule, and DFT calculations have been used to support the identity of the initial product. Upon increasing the partial pressure of propene, additional features corresponding to propane (C3H8) are observed, with the hydrogen-atom source for the observed hydrogenation demonstrated to be additional propene units. Analysis of a systematic increase in the partial pressure of propene in the system demonstrates that the yield of propane correlates with the decrease of the allyl product, demonstrating the H-V(allyl) species as a reactive intermediate in the overall hydrogenation process. An overall mechanism is proposed to rationalize the formation of the insertion product and ultimately the products of hydrogenation, which agrees with previous gas-phase and matrix-isolation work involving propene and the related system, ethene.
A Comparative Analysis of the CO-Reducing Activities of MoFe Proteins Containing Mo- and V-Nitrogenase Cofactors
Lee, Chi Chung,Tanifuji, Kazuki,Newcomb, Megan,Liedtke, Jasper,Hu, Yilin,Ribbe, Markus W.
, p. 649 - 653 (2018/04/16)
The Mo and V nitrogenases are structurally homologous yet catalytically distinct in their abilities to reduce CO to hydrocarbons. Here we report a comparative analysis of the CO-reducing activities of the Mo- and V-nitrogenase cofactors (i.e., the M and V clusters) upon insertion of the respective cofactor into the same, cofactor-deficient MoFe protein scaffold. Our data reveal a combined contribution from the protein environment and cofactor properties to the reactivity of nitrogenase toward CO, thus laying a foundation for further mechanistic investigation of the enzymatic CO reduction, while suggesting the potential of targeting both the protein scaffold and the cofactor species for nitrogenase-based applications in the future.
Tracing the hydrogen source of hydrocarbons formed by vanadium nitrogenase
Lee, Chi Chung,Hu, Yilin,Ribbe, Markus W.
experimental part, p. 5545 - 5547 (2011/07/08)
Hydrocarbons from CO: The vanadium-nitrogenase-catalyzed reduction of carbon monoxide involves the adenosine triphosphate (ATP)-dependent protonation of CO and the subsequent formation of C - C bonds, leading to the production of small hydrocarbons, such as C2H4, C2H 6, C3H6, and C3H8 (see picture). Isotope-substitution studies monitored by GC-MS analysis show that protons are the source of hydrogen for the CO reduction. Copyright
