57384-26-6Relevant academic research and scientific papers
The formation and destruction of H3O-
Miller, Thomas M.,Viggiano, A. A.,Miller, Amy E. Stevens,Morris, Robert A.,Henchman, Michael,et al.
, p. 5706 - 5714 (2007/10/02)
We report the first measurements of rate constants for formation and reaction of the Ion Phys. 49, 311 (1983)>, namely, dehydrogenation of formaldehyde by hydroxide to form hydrated-hydride ion and carbon monoxide.The OD- + H2CO reaction is about 35percent efficient at 298 K, with OD-/OH- exchange occurring in about half the reactions.H3O- was observed to undergo thermal dissociation in a helium carrier gas at room temperature with a rate constant of 1.6 * 10-12 cm3 s-1.We also studied a new reaction in which H3O- is formed: The association of OH- with H2 in a He carrier gas at low temperatures.The rate coefficient for this ternary reaction is 1*10-30 cm6 s-1 at 88 K.Rate coefficients and product branching fractions were determined for H3O- reactions with 19 neutral species at low temperatures (88-194 K) in an H2 carrier.The results of ion-beam studies, negative-ion photoelectron spectroscopy, and ion-molecule reaction data allow us to specify the hydride-water bond energy D0298(H- - H2O) = 14.4+/-1.0 kcal mol-1 (0.62+/-0.04 eV).The heat of formation of H3O-, -37.5+/-1.0 kcal mol-1, and the proton affinity of H3O-, 386.0+/-1.0 kcal mol-1, are derived from these results.Dissociation of H3O- into OH- and H2 requires 4.5+/-1.0 kcal mol-1 energy.
Interaction of metal carbonyl hydrides with Lewis acids
Richmond, Thomas G.,Basoio, Fred,Shriver, Ouward F.
, p. 1624 - 1628 (2008/10/08)
Recent studies on Lewis acid promoted CO migratory insertion to produce metal acyls prompted a comprehensive study of the interaction of metal carbonyl hydrides with molecular Lewis acids. Stable rnetal formyl formation was not achieved in this study, but insight was obtained into reactions that may compete with migratory insertion in metal carbonyl hydrides. The reactivity of metal carbonyl hydrides with strong Lewis acids is dominated by the basic character of the hydride ligand. Variable-temperature multinuclear NMR characterization of the low-temperature complex Mn(CO)5-H-BCl3 is presented. The susceptibility to electrophilic metal hydrogen bond cleavage increases with decreasing acidity of the hydride, Steric factors are also important as evidenced by the observation that H3Re3(CO)12 is much more resistant to eiectrophilic attack than is HRe(CO)5. Also discussed are reactions of Lewis acids with HCo(CO)4, [PPN][HFe(CO)4], [Ir(CO)2(PPh3)2H2][BPh4], HMn(CO)4PPh3, CpMo(CO)3H; and CpMo(CO)2(PPh3)H.
