79264-71-4Relevant academic research and scientific papers
Electrogeneration of Cyanomethyl Anion from Phenylsulphonylacetonitrile and Cyanomethyltrimesitylphosphonium Iodide and the Relative Acidities of XCH2CN (X=Ph3P(1+), Ph3As(1+), Mes3P(1+), or PhSO2) versus Acetic Acid in Acetonitrile
Bellamy, Anthony J.,MacKirdy, Iain S.
, p. 1093 - 1098 (2007/10/02)
Contrary to a previous report, PhSO2CH2CN has been shown to exhibit a one-electron reduction (two-electron reductive cleavage followed by deprotonation of PhSO2CH2CN by (1-)CH2CN).Mes3P(1+)CH2CN I(1-) behaves similarly.The relative acidities of XCH2CN (X= Ph3P(1+), Ph3As(1+), Mes3P(1+), or PhSO2) versus acetic acid in acetonitrile has been studied both voltammetrically and spectrophotometrically.Ph3P(1+)CH2CN is a stronger acid than CH3CO2H; Ph3As(1+)CH2CN, Mes3P(1+)CH2CN, and PhSO2CH2CN are weaker acids than CH3CO2H.PhSO2CH2CN and Mes3P(1+)CH2CN I(1-) have been used in an electroanalytical method for studying the addition of (1-)CH2CN to various electrophiles.
Restricted Rotation in Methyl- and Cyanomethyl-tris-(2,4,6-trimethyl-phenyl)phosphonium Compounds. A 1H Nuclear Magnetic Resonance Spectroscopic Study. The Crystal Structure of Cyanomethyltris-(2,4,6-trimethylphenyl)phosphonium Tetraiodomercurate(II)
Bellamy, Anthony J.,Gould, Robert O.,Walkinshaw, Malcolm D.
, p. 1099 - 1104 (2007/10/02)
The crystal structure of cyanomethyltris-(2,4,6-trimethylphenyl)phosphonium tetraiodomercurate(II), 2*HgI4(2-), is reported, and the bonding and conformational characteristics of the cation are compared with those related structures wich also exist in a propeller conformation.The dynamic stereochemistry of Mes3P(1+)CH2CN, Mes3P(1+)CH3, and Mes3P, as studied by 1H n.m.r. spectroscopy, is described.The calculated ΔG++ values for enantiomerisation of the propeller configuration, assumed to occur via the two-ring flip mechanism, are discussed in the context of related studies.For Mes3P(1+)CH2CN, the enantiomerisation mechanism is related to the conformation in the crystalline state.
