By T. Brent Gunnoe (auth.), Pedro J. Pérez (eds.)
Over the previous decade, a lot study attempt has been dedicated to the layout and synthesis of recent reagents and catalysts that may impact carbon-hydrogen bond activation, normally due to the prospect that C−H activation might let the conversion of inexpensive and considerable alkanes into important functionalized natural compounds.
Alkane C-H Activation by means of Single-Site steel Catalysis offers the present state of the art improvement within the catalytic platforms for the catalytic trans-formations of alkanes below homogeneous stipulations. bankruptcy 1 bargains a entire precis of the most discoveries learned thus far. bankruptcy 2 experiences the so-called electrophilic activation, initiated via Shulpín within the overdue 60s, and the bottom for the Catalytica approach. bankruptcy three examines the catalytic borylation of alkanes, came upon through Hartwig, while bankruptcy four offers an up to date imaginative and prescient of the alkane dehydrogenation response. bankruptcy five covers the oxygenation of C-H bonds, a box of large curiosity with bioinorganic im-plications, and at last bankruptcy 6 offers the functionalization of alkane C-H bonds via carbene or nitrene insertion.
The historical past of C-H bond activation, and the present learn defined during this e-book, spotlight the present learn and current the reader with an outlook of this box which is still explored by way of 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
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.
9 Trifluoroethanol-based model for C–H activation studies pointed out, once again, that we are not necessarily ascribing any mechanistic content to the term). Whereas one might expect the most electrophilic complexes—those with the highest positive charge and/or most electron-withdrawing ligands—to be the most reactive, in fact that is rarely what is found. 9, as the N–N ligand is varied, reflect changes in the equilibrium between the aquo and solvento complexes (only the latter reacts with C–H bonds), rather than affinity for the hydrocarbon substrate .
11 Schematic representation of the inner-sphere mechanism for Pt(II)-Pt(IV) redox reactions be able to compete under Shilov oxidation conditions. It is not at all obvious why it should be so fast. 11; the requirement for an additional X- ligand in the symmetric bridged transition state is responsible for the commonly observed third-order kinetics . Such a mechanism has been demonstrated for N-ligated complexes of the sort used for the model studies described in the previous section [38–40].