Acetonitrile complexes, reaction with

Trifluoromethanesulfonic acid is miscible in all proportions with water and is soluble in many polar organic solvents such as dimethylformamide, dimethyl sulfoxide, and acetonitrile. In addition, it is soluble in alcohols, ketones, ethers, and esters, but these generally are not suitably inert solvents. The acid reacts with ethyl ether to give a colorless, Hquid oxonium complex, which on further heating gives the ethyl ester and ethylene. Reaction with ethanol gives the ester, but in addition dehydration and ether formation occurs. 

The reaction of alkoxyarylcarbene complexes with alkynes mainly affords Dotz benzannulated [3C+2S+1C0] cycloadducts. However, uncommon reaction pathways of some alkoxyarylcarbene complexes in their reaction with alkynes leading to indene derivatives in a formal [3C+2S] cycloaddition process have been reported. For example, the reaction of methoxy(2,6-dimethylphenyl)chromium carbene complex with 1,2-diphenylacetylene at 100 °C gives rise to an unusual indene derivative where a sigmatropic 1,5-methyl shift is observed [60]. Moreover, a related (4-hydroxy-2,6-dimethylphenyl)carbene complex reacts in benzene at 100 °C with 3-hexyne to produce an indene derivative. However, the expected Dotz cycloadduct is obtained when the solvent is changed to acetonitrile [61] (Scheme 19). Also, Dotz et al. have shown that the introduction of an isocyanide ligand into the coordination sphere of the metal induces the preferential formation of indene derivatives [62]. 

A transmetalation of the styrylcarbene chromium complex 62 in the presence of stoichiometric amounts of [Ni(cod)2] to give the nickel carbene intermediate 63 was applied to the synthesis of Cr(CO)3-coordinated cycloheptatriene 64 upon reaction with terminal alkynes [57] (Scheme 37). The formation of pen-tacarbonyl(acetonitrile)chromium is expected to facilitate the metal exchange. 

The Knoevenagel reaction between o-hydroxyaryl aldehydes and ketones and substituted acetonitriles affords high yields of 3-substituted coumarins in aqueous alkaline media <96H(43)1257>, whilst 4-hydroxycoumarins have been elaborated to pyrano [3,2-c]benzopyran-5-ones by reaction with aromatic aldehydes and malononitiile <96P148>. The imine (10) resulting from the complex reaction of o-hydroxyacetophenone with malononitrile undergoes a 1,5-tautomeric shift in solution <96JCS(P1)1067>. 

The reaction mechanism in acetonitrile or water/acetonitrile mixtures occurs with three kineticaUy distinctive steps according to Eqs. (3)-(6), a kinetics significantly more complicated than that observed for the substitution of the aqua ligands in [M3Q4(H20)9f complexes [35, 36]. 

The possible mechanisms for solvolysis of phosphoric monoesters show that the pathway followed depends upon a variety of factors, such as substituents, solvent, pH value, presence of nucleophiles, etc. The possible occurrence of monomeric metaphosphate ion cannot therefore be generalized and frequently cannot be predicted. It must be established in each individual case by a sum of kinetic and thermodynamic arguments since the product pattern frequently fails to provide unequivocal evidence for its intermediacy. The question of how free the PO ion actually exists in solution generally remains unanswered. There are no hard boundaries between solvation by solvent, complex formation with very weak nucleophiles such as dioxane or possibly acetonitrile, existence in a transition state of a reaction, such as in 129, or SN2(P) or oxyphosphorane mechanisms with suitable nucleophiles. 

Anhydrous peroxytrifluoroacetic acid is not easy to handle, but the procedure has recently been revised.121 Namely, reaction of urea-hydrogen peroxide complex (UHP) with tri-fluoroacetic anhydride in acetonitrile at 0 °C gives solutions of peroxytrifluoroacetic acid, which oxidize aldoximes to nitroalkanes in good yields (Eqs. 2.58 and 2.59). Ketoximes fail to react under these conditions, the parent ketone being recovered. 

The red and orange forms of RhCl[P(C6H5)3]3 have apparently identical chemical properties the difference is presumably due to different crystalline forms, and possibly bonding in the solid. The complex is soluble in chloroform and methylene chloride (dichloromethane) to about 20 g./l. at 25°. The solubility in benzene or toluene is about 2 g./l. at 25° but is very much lower in acetic acid, acetone, and other ketones, methanol, and lower aliphatic alcohols. In paraffins and cyclohexane, the complex is virtually insoluble. Donor solvents such as pyridine, dimethyl sulfoxide, or acetonitrile dissolve the complex with reaction, initially to give complexes of the type RhCl[P(C6H6)3]2L, but further reaction with displacement of phosphine may occur. 

Bis[Ar,Ar -di(2-pyridyl)- and -di(2-pyridyl-methyl)-imidazol-2-ylidene]aurate(i) tetrafluoroborates have been prepared from the analogous silver complexes on reaction with (tht)AuCl and their structures determined. The configuration of the cations with sterically well-protected two-coordinate gold centers shows no anomalies. However, fascinating structures are found for the adducts with silver tetrafluoroborate obtained as acetonitrile... 

DDQ ( red = 0.52 V). It is noteworthy that the strong medium effects (i.e., solvent polarity and added -Bu4N+PFproduct distribution (in Scheme 5) are observed both in thermal reaction with DDQ and photochemical reaction with chloranil. Moreover, the photochemical efficiencies for dehydro-silylation and oxidative addition in Scheme 5 are completely independent of the reaction media - as confirmed by the similar quantum yields (d> = 0.85 for the disappearance of cyclohexanone enol silyl ether) in nonpolar dichloromethane (with and without added salt) and in highly polar acetonitrile. Such observations strongly suggest the similarity of the reactive intermediates in thermal and photochemical transformation of the [ESE, quinone] complex despite changes in the reaction media. 

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