Methyl iodide oxidative addition

In the case of phosphine, the active catalyst is presumably either bisphosphine dicarbonyl or the phosphine tricarbonyl complex. Kinet-ically the bis-phosphine nickel complex cannot be the predominant species. However, in the presence of very high phosphine concentration it may have an important role in the catalyst cycle. After ligand loss and methyl iodide oxidative addition, both complexes presumably give the same 5 coordinate alkyl species. 

Feliz M, Freixa Z, van Leeuwen PWNM, Bo C (2005) Revisiting the methyl iodide oxidative addition to rhodium complexes A DFT study of the activation parameters. 

Compound 123 (R = R = H) oxidatively adds chloroform and gem-dichloro-alkanes (940M4153). With methyl iodide, trans addition occurs and species 147 is formed. With dichloromethane, the route is three-fragment and four-electron, and the result is species 148 (R = H). Dichloromelhylbenzene and methyl dichloro-ethanoate give 148 (R = Ph and COOMe, respectively). Simultaneously, the... 

As the formation of the ethyl arsenic acid and the succeeding chlorination of the ethyl arsenious oxide takes place in add conditions, hydriodic acid, which is present in considerable quantity, can form ethyl diiodoarsine. In order to prevent this happening, the iodine is removed as methyl iodide by addition of dimethyl sulphate, which reacts, as discovered by Wieland Ber., 1905, 38, 2327), in the following manner ... 

The one-pot reaction between di(2-bromobenzyl)methylamine (141), n-butyllithium, and antimony trichloride, followed by p-tolyllithium, afforded (142) in 23% yield <88TL5401>. Halogenation of (142) yielded the corresponding dihalides (143 X = Cl, Br or I) and the reaction of (143 X = Cl or Br) with SbCls or AgBp4 resulted in the formation of compounds with Sb—N bonds (144 X = Cl or Br) (Equation (16)). Treatment of (143 X = Cl) with KF in DMF gave the difluoro compound (143 X = F). The structure was assigned to the compounds (143) on the basis of H NMR spectroscopy. The most reasonable structure for (143 X = I) was determined to be the ionic formulation (144 X = I). The addition of benzyltrimethylammonium chloride to (144 X = Cl) converted it back into the neutral compound (143 X = Cl). Methyl iodide oxidatively adds to (142) subsequent reductive elimination of methyl chloride from the intermediate (145) yields the iodostibine (146) in quantitative yield (Equation (17)) <89TL4841>. 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Ewins has synthesised both substances from m-methoxybenzoic acid, which on nitration gave 2-nitro-3-methoxybenzoic acid, and this, on reduction and treatment with methyl iodide, yielded damasceninic acid, which, by esterification with methyl alcohol, furnished damascenine. Kaufmann and Rothlen found that the additive product of 8-methoxy-quinoline and methyl sulphate, on oxidation with permanganate, yields formyldamasceninic acid, MeO. CgH3(NMe. CHO). COOH, which can be transformed into damasceninic acid by warming with dilute hydrochloric acid. ... 

Polymer-bound phenyliodine difluoride, which also has been used as a reagent to add fluorine to alkenes, can be prepared by the addition of xenon difluoride to the polymer [134, 135 136] Methyl iodide is converted to trifluoro methyliodine difluoride by treatment with fluorine at -110 C [137] Perfluoro-alkyliodine tetrafluorides could be synthesized from the perfluoroalkyliodine difluorides and fluorine [138] or chlorine trifluoride [139] Perfluoroalkyl [140] and perfluoroaryl [141] iodides are oxidized to the corresponding iodine difluorides by chlorine trifluoride. 

Oxidative addition of XY substrates to [IrL2(/x-pz)]2 [La = (CO)2, cod] and [Ir(CD)(PPh3)(/i,-pz)]2 occurs via a two-center, two-electron route toward the iridium-iridium bond-containing species 131 (960M3785 980M2743). Complex 132, which is prepared by the ligand-substitution reaction from [Ir(CO)2 (/x-pz)]2, adds methyl iodide to give 133. 

The 3,5-bis(trifluoromethyl)pyrazolate analog [Ir(cod)(/x-3,5-(CF3)2pz)]2 does not enter into oxidative addition with iodine, methyl iodide, or acetylenes. The mixture of pyrazolate and 3,5-bis(trifluoromethyl)pyrazolate gives [(rj -codllrf/x-pz)(/L-3,5-(CF3)2pz)Ir(rj -cod)], which reacts with bis(trifluoromethyl)acetylene in a peculiar manner [83JCS(CC)580], producing 145, where 3,5-bis(trifluoromethyl) pyrazolate is replaced by the ethylene bridge and the rj -coordination mode of one of the cod ligands is converted into the rj -allylic mode. 

Oxidation of the alkaloid Glaucin (136) resulted in the formation of a yellow alkaloid 137, which seemingly is contained in Glaucium flavum var. vestitum (Scheme 48). Addition of methyl iodide converted this compound via a methylation/ether cleavage sequence into Corunnine (127) and small amounts of Pontevedrine (138) which is not a mesomeric betaine (71TL3093). 

The mechanism of the carhonylation reaction is thought to involve a frrst-step oxidative addition of the methyl iodide promotor to the Rh(I) complex, followed hy a carhonyl cis insersion step ... 

As shown in Scheme 168, oxidative addition reactions with either methyl chloride or methyl iodide proved successful and yielded the corresponding octahedral rhodium(III) complexes. ... 

The presence of redox catalysts in the electrode coatings is not essential in the c s cited alx)ve because the entrapped redox species are of sufficient quantity to provide redox conductivity. However, the presence of an additional redox catalyst may be useful to support redox conductivity or when specific chemical redox catalysis is used. An excellent example of the latter is an analytical electrode for the low level detection of alkylating agents using a vitamin 8,2 epoxy polymer on basal plane pyrolytic graphite The preconcentration step involves irreversible oxidative addition of R-X to the Co complex (see Scheme 8, Sect. 4.4). The detection by reductive voltammetry, in a two electron step, releases R that can be protonated in the medium. Simultaneously the original Co complex is restored and the electrode can be re-used. Reproducible relations between preconcentration times as well as R-X concentrations in the test solutions and voltammetric peak currents were established. The detection limit for methyl iodide is in the submicromolar range. 

Substantially more work has been done on reactions of square-planar nickel, palladium, and platinum alkyl and aryl complexes with isocyanides. A communication by Otsuka et al. (108) described the initial work in this area. These workers carried out oxidative addition reactions with Ni(CNBu )4 and with [Pd(CNBu )2] (. In a reaction of the latter compound with methyl iodide the complex, Pd(CNBu )2(CH3)I, stable as a solid but unstable in solution, was obtained. This complex when dissolved in toluene proceeds through an intermediate believed to be dimeric, which then reacts with an additional ligand L (CNBu or PPh3) to give PdL(CNBu )- C(CH3)=NBu I [Eq. (7)]. 

Oxidative addition of methyl iodide to coordinatively unsaturated, low-oxidation state d and [Pg.321]

Abdou, H.E., Mohamed, A.A. and Fackler, J.P. Jr (2004) Oxidative addition of methyl iodide to dinuclear Gold(I) amidinate complex schmidbaur s breakthrough reaction revisited with amidinates. ZeitschriJiJurNaturforschungB. A Journal of Chemical Sciences, 59, 1480-1482. 

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