Cummins, Daniel C.; Alvarado, Jessica G.; Zaragoza, Jan Paulo T.; Effendy Mubarak, Muhammad Qadri; Lin, Yen-Ting; de Visser, Sam P.; Goldberg, David P. published the artcile< Hydroxyl Transfer to Carbon Radicals by Mn(OH) vs Fe(OH) Corrole Complexes>, Safety of Triphenylmethanol, the main research area is manganese iron corrole complex hydroxyl transfer tertiary carbon radical.
The transfer of •OH from metal-hydroxo species to carbon radicals (R•) to give hydroxylated products (ROH) is a fundamental process in metal-mediated heme and nonheme C-H bond oxidations This step, often referred to as the hydroxyl “”rebound”” step, is typically very fast, making direct study of this process challenging if not impossible. In this report, we describe the reactions of the synthetic models M(OH)(ttppc) (M = Fe (1), Mn (3); ttppc = 5,10,15-tris(2,4,6-triphenyl)phenyl corrolato3-) with a series of triphenylmethyl carbon radical (R•) derivatives ((4-X-C6H4)3C•; X = OMe, tBu, Ph, Cl, CN) to give the one-electron reduced MIII(ttppc) complexes and ROH products. Rate constants for 3 for the different radicals ranged from 11.4(1) to 58.4(2) M-1 s-1, as compared to those for 1, which fall between 0.74(2) and 357(4) M-1 s-1. Linear correlations for Hammett and Marcus plots for both Mn and Fe were observed, and the small magnitudes of the slopes for both correlations imply a concerted •OH transfer reaction for both metals. Eyring analyses of reactions for 1 and 3 with (4-X-C6H4)3C• (X = tBu, CN) also give good linear correlations, and a comparison of the resulting activation parameters highlight the importance of entropy in these •OH transfer reactions. D. functional theory calculations of the reaction profiles show a concerted process with one transition state for all radicals investigated and help to explain the electronic features of the OH rebound process. Hydroxyl transfer is a critical step catalyzed by metallo-oxygenases. Rates of hydroxyl transfer for FeOH and MnOH heme analogs with tertiary carbon radical derivatives show that FeOH reactivity is more sensitive to the electronic structure of the substrate. Variable temperature kinetic anal. and DFT calculations indicate a highly ordered transition state and a significant role for entropy in the activation barriers.
Inorganic Chemistry published new progress about Activation enthalpy. 76-84-6 belongs to class alcohols-buliding-blocks, and the molecular formula is C19H16O, Safety of Triphenylmethanol.
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