By T. Brent Gunnoe (auth.), Pedro J. Pérez (eds.)
Over the earlier decade, a lot examine attempt has been dedicated to the layout and synthesis of latest reagents and catalysts which can impact carbon-hydrogen bond activation, normally as a result prospect that C−H activation might allow the conversion of inexpensive and ample alkanes into necessary functionalized natural compounds.
Alkane C-H Activation by means of Single-Site steel Catalysis provides the present state of the art improvement within the catalytic structures for the catalytic trans-formations of alkanes less than homogeneous stipulations. bankruptcy 1 deals a accomplished precis of the most discoveries learned to date. bankruptcy 2 reports the so-called electrophilic activation, initiated via Shulpín within the overdue 60s, and the bottom for the Catalytica method. bankruptcy three examines the catalytic borylation of alkanes, came across via Hartwig, while bankruptcy four presents an up to date imaginative and prescient of the alkane dehydrogenation response. bankruptcy five covers the oxygenation of C-H bonds, a box of huge curiosity with bioinorganic im-plications, and eventually bankruptcy 6 offers the functionalization of alkane C-H bonds by way of carbene or nitrene insertion.
The heritage of C-H bond activation, and the present examine defined during this ebook, spotlight the present study and current the reader with an outlook of this box which remains to be explored through an more and more visionary and enthusiastic team of natural, organometallic, organic and actual chemists.
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Extra info for Alkane C-H Activation by Single-Site Metal Catalysis
16 indicated that [PtCl4]2- is not capable of oxidizing [PtCl3(CH3)]2- competitively with protonolysis at room temperature , but if the same temperature trends hold here as for oxidation by [PtCl6]2-, at operating Shilov temperatures Eq. 11 could well be a competent mechanism for Pt metal formation. Â II Ã2À Â II Ã2À Â Ã2À Pt Cl3 ðCH3 Þ þ Pt Cl4 À! PtIV Cl5 ðCH3 Þ þPt0 þ 2ClÀ ð2:11Þ 36 J. A. Labinger In the following sections we will examine potential applications, of both the original Shilov system and modifications thereof, within the context of this welldelineated mechanistic framework.
3) . 5 times as reactive as the hydroxymethyl group. 5 . 17:1 was deduced . However, that result is complicated by the tendency of platinum metal to precipitate from Shilov reactions, especially when carried out in pure water. 4 Proposed three-step Shilov oxidation sequence for the oxidation of methane to methanol/methyl chloride variety of oxidants, including [PtCl6]2- , so that if colloidal (and hence not visible) Pt were present during this experiment (and, likewise, in any of those discussed above), the apparent reactivity of methanol would be artificially high.
By extrapolation, oxidation should be even more dominant around 120 °C, more typical of Shilov conditions. 16 Reactions used to determine relative rates of oxidation and protonolysis of an (alkyl)Pt(II) complex at elevated and room temperatures activation (step 1)[oxidation (step 2)[protonolysis (reverse of step 1). That may not be unreasonable; one might expect protonolysis to have a low activation barrier. It should be noted, however, that these two studies were carried out in different media, water and aqueous acetic acid respectively.