130036-39-4Relevant academic research and scientific papers
Kinetic hydricity of transition-metal hydrides toward trityl cation
Cheng,Bullock
, p. 4031 - 4033 (2008/10/09)
The kinetics of hydride transfer from a series of metal hydrides (MH) to Ph3C+BF4- (producing Ph3-CH and M - FBF3) have been studied by stopped-flow methods in CH2Cl3 solution. Second-order rate constants at 25°C span 5 orders of magnitude in kinetic hydricity, ranging from k = 5.0 × 101M-1 s-1 for HMn-(CO)5 to k = 4.6 × 105 M-1 s-1 for trans-HMo(CO)2-(PMe3)Cp.
Mechanistic studies of the oxidative cleavage of the molybdenum-mercury bonds in [CpMo(CO)2(PPh3)]2Hg
Lin, Chen C.,Gipson, Stephen L.
, p. 167 - 172 (2008/10/08)
Chemical or electrochemical oxidation of the trimetallic complex [CpMo(CO)2(PPh3)]2Hg (Cp = η5-C5H5) occurs in two one-electron steps. The first electron transfer generates a transient cation which undergoes Mo-Hg bond cleavage to generate a 16-electron species, [CpMo(CO)2(PPh3)]+, and a mercury-centered radical, CpMo(CO)2(PPh3)Hg?. To account for the products, it is proposed that the radical dimerizes and then reacts with half of the available 16-electron cation to form an observable pentametallic intermediate. The second electron transfer generates [CpMo(CO)2(PPh3)Hg]+ and returns the 0.5 mol of [CpMo(CO)2(PPh3)]+ which was incorporated into the intermediate. The mercury-containing cation subsequently eliminates metallic mercury to yield a second mole of [CpMo(CO)2(PPh3)]+. The 16-electron cation coordinates solvent or other available neutral or anionic ligands to yield 18-electron complexes.
