Alkane C-H Activation by Single-Site Metal Catalysis by T. Brent Gunnoe (auth.), Pedro J. Pérez (eds.)

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 recent reagents and catalysts that could effect carbon-hydrogen bond activation, quite often end result of the prospect that C−H activation may let the conversion of inexpensive and considerable alkanes into helpful functionalized natural compounds.

Alkane C-H Activation by means of Single-Site steel Catalysis provides the present cutting-edge improvement within the catalytic platforms for the catalytic trans-formations of alkanes lower than homogeneous stipulations. bankruptcy 1 deals a entire precis of the most discoveries learned up to now. bankruptcy 2 reports the so-called electrophilic activation, initiated by way of Shulpín within the past due 60s, and the bottom for the Catalytica method. bankruptcy three examines the catalytic borylation of alkanes, chanced on 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 at last bankruptcy 6 offers the functionalization of alkane C-H bonds by way of carbene or nitrene insertion.

The historical past of C-H bond activation, and the present examine defined during this publication, spotlight the present learn and current the reader with an outlook of this box which remains to be explored by way of an more and more visionary and enthusiastic crew of natural, organometallic, organic and actual chemists.

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A possible example is the combination of [Pt(Mebpym)Cl2]+ (where Mebpym is derived from the bipyrimidine ligand discussed in the next section by methylation at one of the non-coordinated N centers) and the polyoxometalate H5PV2Mo10O40, supported on silica; that system was reported to catalyze oxidation of methane at 50 °C by O2, giving some methanol and (mostly) acetaldehyde, with up to 30 turnovers [53]. The formation of acetaldehyde, a quite unexpected product, has not been completely explained.

14). While there is no way to distinguish between these two possibilities, the former seems clearly favored by the fact that it is the microscopic reverse of the first step of many examples of oxidative addition of methyl halide to square-planar, four-coordinate d8 complexes [42]. Àd½RPtIV Š k1 ½ClÀ Š þ k2 ½H2 OŠ ¼ dt 1 þ K ½ClÀ Š ð2:10Þ Conclusive evidence supporting the nucleophilic attack mechanism was obtained from a stereochemical study. 15), demonstrating inversion of configuration, as expected for SN2 [42].

While the calculated transition state for an oxidative addition route came out very close in energy, the authors preferred the r-CAM, feeling that a Pt(IV) intermediate was unlikely [25]. Subsequent calculations by Ziegler included all possible chloro(aquo)Pt(II) species; they concluded that the neutral PtCl2(H2O)2 is the most reactive, but depending on conditions it may be present in 26 J. A. Labinger Fig. 1 Calculated transition state for activation of methane by PtCl2(H2O)2. Reprinted from Ref.

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