Carbon-hydrogen bond activation by

Arndtsen, B.A., Bergman, R.G., Mobley, T.A. and Peterson, T.A. (1995) Selective intermolecular carbon—hydrogen bond activation by synthetic metal complexes in homogeneous solution. Acc. Chem. Res., 28, 154. 

W. D. Jones, and F. J. Feher, Alkane Carbon-Hydrogen Bond Activation by Homogeneous Rhodium(I) Compounds, Organometallics 2, 562-563 (1983). 

Lyons, J. E. Selective oxidation of hydrocarbons via carbon-hydrogen bond activation by soluble and supported palladium catalysts. Catal. Today 3,245-258. 

Jones WD, Feher FJ (1983) Alkane carbon-hydrogen bond activation by homogeneous rhodium compounds. OrganometaUics 2 562-563... 

Probing the mechanism of carbon-hydrogen bond activation by photochemically generated hydridotris-(pyrazolyl)borato carbonyl rhodium complexes New experimental and theoretical investigations... 

Carbon-hydrogen bond activation by transition metals has found its way to becoming an important aspect of organic synthesis. Metals have been found to break C-H bonds and then participate in follow-up reactions, oftentimes insertions of olefins or alkynes, that permit functionalization of a substrate or the formation of fused-ring systems. As this chemistry is developed, it is clear that selectivity in C-H bond activation is a critical issue that must be controlled to make a given functionalization reaction valuable. 

Bulls, A. R. Carbon-hydrogen bond activation by peralkylhafnocene and peralkylscandocene derivatives. Ph.D. Thesis, Cafifomia Institute of Technology, Pasadena, CA, 1988. 

J. E. Lyons, Catal. Today, 1988, 3, 245-258. Selective Oxidation of Hydrocarbons Via Carbon-Hydrogen Bond Activation by Soluble and Supported Palladium Catalysts. R. Rossi, Bioact. Mol, 1988, 7, 29-45. Highly Selective Syntheses of Naturally-Occurring Acetylenes and Their Structural Analogs by Palladium-Catalyzed Carbon-Carbon Bond Eorming Reactions. 

Cundari TR, Klinckman TR, Wolczanski PT. Carbon—hydrogen bond activation by titanium imido complexes. Computational evidence for the role of alkane adducts in selective C—H activation. J Am Chem Soc. 2002 124 1481—1487. 

Carbon-hydrogen bond activation by. a number of Re complexes has been reported. In the case of CpRe(PMe3)3 photochemical displacement led to C-H activation of both alkenes and alkynes at low temperatures and cyclometallation products at higher temperatures. With Cp Re(CO)(PMe3)N2, photochemical activation via N2 loss led to activation of C-H bonds. ... 

Arndtsen BA, Bergman RG, Mobley TA, Peterson TH. Selective intermolecidar carbon-hydrogen bond activation by synthetic metal complexes in homogeneoias solution. 

The addition of hydrogen cyanide (HCN) to carbon-carbon double bonds activated by electron-withdrawing groups in the presence of a base as a catalyst (a variation of the Michael Reaction) has been known for a long time. Nitriles were also obtained by hydrocyanation of branched olefins, such as isobutylene and trimethylethylene, in vapor phase reactions in particular the reactions over alumina (3) and cobalt-on-alumina (4) were reported in the late 1940s and early 1950s. Addition of HCN to conjugated dienes in the presence of cuprous salts (vapor and liquid phase) was reported as early as 1947 (5). 

Shilov chemistry, developed from 1970, employs [Pt(II)CLt] salts to oxidize alkanes RH to ROH or RCl with modest efficiency. Pt(IV) is an efficient (but economically impractical) primary oxidant that makes the process catalytic. This discovery strongly contributed to the continuing activity in CH activation. Periana developed a related and much more efficient system for methane oxidation to methanol using 2,2 -bipyrimidine ligands and sulfuric acid as solvent. In this case, the sulfuric acid is the primary oxidant and the methanol formed is protected by being converted in situ to MeOSOsH, an ester that strongly resists further oxidation. This area is more fully described under the entry Alkane Carbon-Hydrogen Bond Activation. 

Alkane Carbon-Hydrogen Bond Activation), such behavior might not be expected of a monophosphine. However, in the reaction of [Rh(/u.-Cl)(COE)2]2 with four equivalents of PhCH2CH2PBu 2, this is observed as the product in (18) and conversion to (19) occurs on chloride abstraction (see also (174), Section 42). " A related situation is obtained when [Rh(/x-Cl)(Bu 2PCH2PBu 2)]2 is treated with neopentyl lithium where the highly unsaturated, 14-electron metal in the product, (20), is stabilized by an agostic interaction. ... 

The complexes containing chelating phosphines are much more stable than their PMes analogues. Carbon-hydrogen bond activation can be achieved by reaction of RuH(03SMe)(dmpm)2 with AlMes in benzene. The sole product isolated from this reaction is RuH(Ph)(dmpm)2. If the reaction is carried out in toluene, the RuH(CH3C6H4)(dmpm)2 eomplex is isolated". 

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