92204-03-0Relevant academic research and scientific papers
Heterogenous rediction of (diolefin)dialkylpatinum(ii) complexes on platinum black in ethyl alcohol: Kinetics isotopic interchange of hydrogen between coadsorbed surface alkyls, and comparison of surface alkyls generated from the platinum complexes and from olefins
Randell Lee,Whitesides, George M.
, p. 2576 - 2585 (2007/10/02)
This paper reports an investigation of the heterogeneous hydrogenations of (diolefin)dialkylplatinum(II) complexes ((DO)PtR2) catalyzed by platinum black in ethyl alcohol The organic of (DO)PtR2 complexes are converted to via intermediate surface alkyls, and the platinum(II) is ipcorporated into the surface of the catalyst as platinum(0). These reductions exhibit two kinetic regimes: in the first, the rate of reaction is limited by the mass transport of hydrogen to the surface of the catalyst (the mass-transport-limited regime, MTL); in the second, the rate is limited by a reaction on the surface of the catalyst (the reaction-rate-limited regime, RRL), In reductions of (DO)PtRz complexes in n-hexane, interchange of H/D occurs between the surface alkyls derived from the diolefin and those derived from the R groups; in reductions in ethyl alcohol (EtOH), this interchange is eliminated by rapid exchange between D* and (EtOH). Under RJRL conditions, the distributions of ethanes-dn, produced from the reductions of (1,5-cyclooctadiene)diethylplatinumCII) ((COD)PtEtj) and of ethylene that the R* from and from platinum have relative of (and thus of C-H bond activation) and reductive elimination as alkane. Comparison of the distributions of propanes-dn, produced from the reductions under RRL conditions of (1,5-cyclooctadiene)di-n-propylplatinum(II), of (1,5-cyclooctadiene)diisopropylplatinum(ll), and of propylene to the conclusion. Under MTL conditions, the Et* moieties derived from (COD)PtEt2 have a slower rate of C-H bond activation (relative to the rate of reductive elimination) than these derived from ethylene, of the R* to be that of the cyclooctyl* in.
