Activation of simple alkanes by a platinum(II) complex; homogeneously catalysed hydrogen–deuterium exchange

A kinetic investigation of the insertion of ketones into the dioxygen adduct dioxobis(triphenylphosphine)platinum

“…This is a facile reaction probably because the electrophilic character of the carbon atom of the carbonyl group is enhanced by the coordination to the platinum center. 13 The order of reactivity that we have found (when steric effects are not too important) is in good agreement with that reported for reactions with other classical nucleophiles,14•15 i.e., 1,1,1 -trifluoroacetone » ace- [DMF], M Figure 4. Plots of 1 /&a and 1 jkb vs. dimethylformamide concentration for the reaction with acetone in benzene at 30 ±0.1 °C, [(PPh3)2Pt02] = (1.4 ± 0.3) 10-3 M.…”

Shilov alkane platinum chemistry: 45 years

“…Since about two years after our first publications there had not been any responses to them among the chemical community, an appearance of Hodges and co-authors's papers [6,7] in British journals in 1971 on H/D exchange on platinum complexes was met, at least by me, with great excitement. For Hodges it was a natural continuation of his works with Garnett on H/D exchange of aromatic compounds but nevertheless they greatly appreciated our results: "This is a significant observation.…”

“…For Hodges it was a natural continuation of his works with Garnett on H/D exchange of aromatic compounds but nevertheless they greatly appreciated our results: "This is a significant observation. For the first time activation under homogeneous conditions appears to have occurred in an alkane, and it could represent a significant step in the use of transition-metal complexes as catalysts for reactions of the alkanes" [6]. Hodges suggested a mechanism for H-D exchange in which an alkane first binds to platinum followed by C-H cleavage.…”

Activation entropy as a dominant factor in the oxidative addition of some group IV hydrides to an iridium(I) complex

“…It is of interest that the only reported examples of catalytic activation of paraffins use such an approach (11,12). In the case of hydrogen activation by halo-complexes of the group VlHI metals in aqueous media, the reactions characteristically exhibit quite favorable entropies of activation, but prohibitive enthalpies (1 3).…”