Acetonitrile copper

Ferrocenyltriphenylphosphonium perchlorate (84) has been synthesized from iodoferrocene, tetrakis(acetonitrile)copper(i), and triphenylphosphine in nitromethane. The authors suggest that iodoferrocene first forms the complex (85) which then breaks down via a four-centred transition state to (84). 

Benzene-1,2-diamine derivatives 9 react with tetrakis(acetonitrile)copper(l) tetrafluoroborate via smooth cyclization and aromatization to afford quinoxaline derivatives 10. ... 

Ring expansion of cyclic ketones. A new method for expansion of cyclic ketones to the expanded a-dithioketals involves addition of (CH3S)3CLi followed by treatment of the adduct with tetrakis(acetonitrile)copper(I) perchlorate or tetra-fluorohorate.2... 

Based on this scheme, the kinetics of decomposition of diazodiphenylmethane and diazofluorene in acetonitrile by ZnCl, ZnBr or Znij has been explained Copper complexes of type 416 or 417 have been invoked to account for kinetics and products of the decomposition of diazodiphenylmethane by CuBr in acetonitrile Copper carbenoids of unspecified structure were assumed in analogous investigations with CuBr and CuClO [but not with CufClOJ which initiates a radical cation pathway, vide infra]. Carbenoids 416 (X = Hal) have been isolated from reactions... 

Similarly, the nitrene transfer reaction from 128 is facilitated by a variety of catalysts, including MTO (136) <01JCS(CC)235>, the lri(pyrazolyl)borate-coppcr(l) complex 137 <01OL1423>, and tetrakis(acetonitrile)copper(I) hexafluorophosphate (138) <01JA7707>. In the latter case, the reaction can be carried out using a sulfonamide and the primary oxidant, iodosylbenzene, whereby the actual nitrene transfer reagent 128 is presumed to be formed in situ. In all cases, acetonitrile appears to be the solvent of choice. 

The yields in the classical variant are rarely as high as that for diphenic acid. However, tetrakis(acetonitrile)copper(l) perchlorate and similar organic solvent soluble copper(l)... 

A solution of 4-nitrophenyldiazonium tetrafluoroborate (60, 237 mg, 1 mmol) in acetone (300 ml) was added dropwise to the stirred solution of tetrakis(acetonitrile)copper(l) perchlorate (165 mg, 5 mmol, 5 eq.) and copper(ll) perchlorate tetrahydrate (135 mg, 4 mmol, 4 eq.) in acetone (200 ml) containing acetonitrile (3.75 ml, 0.75 vol%) and water (16 pi, 0.9 mmol) at 25 °C under nitrogen. The reaction mixture was stirred for 30 minutes, diluted with diethyl ether (20 ml) and 5% aqueous ammonia solution (20 ml). The resulting mixture was stirred for 10 min. The aqueous layer was separated and extracted with diethyl ether (5x20 ml). The combined organic phases were dried (Na2S04), and evaporated to dryness. The residue... 

Related Reagents. Copper(II) Trifluoromethanesulfonate Copper(I) Iodide Tetrakis(acetonitrile)copper(I) Hexafluoro-phosphate Tetrakis(acetonitrile)copper(I) Perchlorate. 

Copper-based complexes have been found to be excellent catalysts for the aziiidination of alkenes employing PhI=NTs as the nitrene precursor (eq 12). Both Cu and Cu efficiently catalyze the reaction, and the hest results are usually obtained with the cationic complexes tetrakis(acetonitrile)copper(I) perchlorate and copper(n) trifluoromethanesulfonate Good yields are obtained with a variety of substrates, including aliphatic alkenes and enolsUanes (eq 13), the latter delivering a-amino ketones upon hydrolysis of the intervening sUyloxyaziridine. 

Soleimani, E. Khodaei, M. M. Batooie, N. Samadi, S. Tetrakis(acetonitrile)copper(I) hexafluorophosphate catalyzed coumarin synthesis via Pechmann condensation under solvent-free condition. J. Heterocycl. Chem. 2012, 49, 409-412. 

Metal ions other than Ag+ and Hg2+ serve as useful oxidants in preparative coordination chemistry. Eor example, it is well known that coordination of MeCN stabilizes copper(I) complexes, which are otherwise prone to disproportionation to copper(O) and copper(II). Accordingly, in acetonitrile, copper(II) ions are found to be oxidants capable of oxidizing for example, tetrathiafulvalene 09 or 2,2 -bithiophene, ° with concomitant formation of copper(I). 

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