2,6-Dimethylphenyl isocyanide

Yamamoto and Yamazaki also suggest that the higher steric requirements of tert-h xty and 2,6-dimethylphenyl isocyanides determine the lack of an acylimino-nickel complex in their reactions with C5H5Ni(PPhj)CH3 (166). 

The adsorption mode of 2,6-dimethylphenyl isocyanide (DMPl) on Au electrodes [43] has been studied using potential-dependent SERS. The gold substrate... 

The mode of 2,6-dimethylphenyl isocyanide (DMPI) adsorption on Pt electrodes [43] has been studied using potential-dependent SERS. The Pt electrodes were obtained by depositing Pt nanoparticles ( 17nm) on a polycrystalline Pt film. Three bands appear, at 2166, 2124 and 1997cm" , when DMPI is adsorbed on the... 

A DFT study on the GaCl3-catalysed 4 + 1-cycloaddition of a -unsaturated ketones with 2,6-dimethylphenyl isocyanide to produce unsaturated lactones shows the reaction is stepwise and exothermic.224,225... 

Cyclization of diynes to iminocyclopentadienes. 1,6-1,8-Diynes cyclize with 2,6-dimethylphenyl isocyanide when treated with Ni(COD)2, 1 equiv., to form bicy-... 

A three-component one-pot coupling of 2,6-dimethylphenyl isocyanide, methyl 2,4-dioxopentanoate and alkynoic esters leads to the isatin-like compounds (or fused pyrans) 20 (Scheme 5). The reaction proceeds by initial formation of the zwitterionic intermediate 21, which is protonated by methyl 2,4-dioxopentanoate. Attack of the newly generated nucleophile then forms the intermediate 22. The pyrrolidinone ring is formed upon loss of methanol and electrocyclization then occurs to afford the desired 2//-pyrans (Scheme 5) <2005S1049>. 

The reaction of 2,6-dimethylphenyl isocyanide 70 with the disilene 10 gives the disi-lacyclopropane imine 7188, the unusually bright red color of which was the subject of an intensive theoretical investigation (equation 13)89. 

The reaction between 133 and THF or adamantyl cyanide afforded the base adducts 139 and 140, respectively. Complex 140 was characterised by X-ray crystallography and in the solid state one chloride was found to be trans to the methandiide centre, mutually cis to the other chloride which was in turn trans to the coordinated nitrile. The base adduct 141 resulted from the addition of 2,6-dimethylphenyl isocyanide to 132. Neither 139 or 141 were characterised in the solid state so it is not known which geometric isomers were formed. 

The 1,3-dipolar addition of phenylazide to metal coordinated ligands affords carbodi-imide ligands. An example is the reaction of the bis-azidopalladium complex 38 with two equivalents of 2,6-dimethylphenyl isocyanide to give the bis-carbodiimide complex 39. ... 

Insertion of isonitriles into zirconacycles affords )] -iminoacyl complexes that smoothly rearrange to stable f-irame zirconocenes. In the case of 2-phosphanozirconaindenes, rearrangement proceeds leading to -imine zirconocenes (Scheme 35). Subsequent formation of a /3-phosphano indenoimine is obtained by elimination of Cp2Zr fragment for the 2,6-dimethylphenyl isocyanide." ... 

Phosphorane (64) can be isolated in pure form when diphenylcyclopropenone is treated with triphenylphosphine. This product arises, at least formally, by interception of the ring-opened species 49 by the phosphine. It can be decomposed by methanol to methyl a-phenylcinnamate and triphenylphosphine. Isocyanides such as 2,6-dimethylphenyl isocyanide react with 64 to yield the interesting product 65, an imine of cyclobutenedione (equation 60). ... 

A number of titanium derivatives containing carbazole ligands have been isolated. Reaction of Ti(GH2Ph)4 with carbazole yields the dibenzyl complex Ti(GH2Ph)2(cb)2 (Scheme 45). The reaction of this compound with 2,6-dimethylphenyl isocyanide leads to titanium derivatives containing new carbon-carbon bonds (Section 4.05.2.3).109,110... 

The reactions of Ti(CH2Ph)2(cb)2 and (cb)2Ti(/x-CHSiMe3)2Ti(cb)2 (cb = carbazole) with 2,6-dimethylphenyl isocyanide lead to titanium derivatives containing new carbon-carbon bonds (Scheme 130). The molecular structures of the insertion products have been determined by X-ray diffraction.109 Reaction of Ti(CH2Ph)2(cb)2 with 2,6-dimethylphenyl isocyanide (xylNC) gives the double insertion product bis(iminoacyl) derivative. The iminoacyl... 

Complex 77 reacts rapidly with 1 equiv. of 2,6-dimethylphenyl isocyanide to form the monoinsertion 72-iminoacyl product 7990 (Scheme 15). A toluene solution of 24/79 undergoes elimination of /ra t-2-benzylstyrene at room temperature over several hours, yielding the terminal Zr imido complex 25/80. Complex 80 adopts a tbp geometry, with the imido ligand occupying an equatorial site. The transformation of the 72-iminoacyl 24/79 to the terminal imido 25/80 is unique, presumably occurring via a retro [2 + 2]-cycloaddition from an azametallacyclobutane intermediate. 

Refluxing three equivalents of 2,6-dimethylphenyl isocyanide with 2,3-diphenylcyclopropenone in benzene for 4 hours under a stream of nitrogen resulted in the formation of 4,5-bis(2,6-dimethylphenylimino)-2,3-diphenylcyclopent-2-enone (1) in 76% yield. When the reaction of 2,3-diphenylcyclopropenone with a molar equivalent of 2,6-dimethylphenyl isocyanide was carried out in the presence of a catalytic amount of triphenylphosphane in benzene for 24 hours at 20 "C under nitrogen, 4-(2,6-dimethylphenylimino)-2,3-diphenylcyclobut-2-enone(2) was obtained in 84% yield. " ... 

Dimethylphenyl isocyanide (0.132 g, 1 mmol) in solution in 3 mL of toluene was added via a double tipped needle to the solution prepared above and stirred overnight at room temperature. Solvents were evaporated to dryness and the solid residue was extracted with pentane (3 x 50 mL) and filtered on Celite 5 g. Enantiopure ligands 1(RP) or 1(SP) were obtained as yellow solids in 72% yield (0.276 g) after solvent removal. 

A common problem associated with the use of metal carbonyls as synthetic reagents is the drastic conditions required to induce CO dissociation. Catalytic amounts of a variety of transition metal complexes have been found to induce stepwise CO substitution (35). Thus Fe(CO)5 reacts with 2,6-dimethylphenyl isocyanide only in the presence of catalytic CoCl2 to give Fe(RNC)(CO)4. The data are consistent with the mechanisms presented in Scheme 3. 

At room temperature, treatment of 2-6a with 1.2 equivalents of aliphatic isocyanide t-BuNC led to the mono-insertion of isocyanide into the Zr-C(sp ) a bond giving 2-14a in 91 % isolated yield (Scheme 2.10a). Even in the presence of excess amount of t-BuNC, only 2-14a was obtained and the double-insertion product was not observed, probably due to the steric hindrance of t-Bu group. Similarly, the insertion of t-BuNC into tolyl-substituted 2-6b gave 2-14b under the same condition (Scheme 2.10b). However, when 2.4 equivalents of less steric-hindered isocyanide CyNC were used, the double-insertion product 2-15 was formed exclusively in 78 % isolated yield (Scheme 2.10b), showing that the steric hinderance of isocyanides strongly affects the insertion reaction. The double-insertion product 2-16 could also be obtained in good isolated yield when 2.4 equivalents of 2,6-dimethylphenyl isocyanide were used to react with 2-6a (Scheme 2.10c). It should be noted that... 

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