N. Soundararajan

Activation parameters for the reaction of phenylchloro carbene with pyridine, tri-n-butyltin hydride, and triethylsilane; evidence against the need to invoke reversibly formed complexes in the reaction of this carbene with olefins

Abstract The activation energies for reaction of phenylchloro carbene with pyridine, tri-n-butyl-tin hydride and triethylsilane are reported. The data argues against reversibly formed complexes in the reaction of this carbene with olefins.

Kinetics and spectroscopy of ylids from reaction of p-substituted phenylchlorocarbenes with acetone

Abstract Laser flash photolysis of p-CF 3 and p-Cl-phenylchloro diazirines produces the corresponding carbenes which react with acetone to produce easily detected ylids. The absolute rate constants of reaction of these carbenes with acetone, and the rate constants of reaction of the ylids with diethylfumarate have been determined. No reaction was found between these carbenes and simple esters or ethylene carbonate.

EPR spectroscopy of a diaza derivative of meta-xylylene

Abstract Photolysis of 2,4,6-trifluoro-1,3-diazidobenzene in 2-methyltetrahydrofuran at 77K produces a dinitrene quintet. Upon warming the quintet briefly to look followed by recooling to 77K the EPR spectrum of the quintet disappears and is replaced by that of a trifluorodiaza biradical.

Photochemical cleavage of benzylic stannanes

Abstract Photolysis of benzylic stannanes leads to efficient homolytic cleavage to form benzylic and stannyl radicals. The reaction proceeds via the excited singlet state of the benzyl stannane.