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Generation, Reactions, and Kinetics of Sterically Congested Triplet Diphenylcarbenes. Effects of Bromine Groups

2001; American Chemical Society; Volume: 124; Issue: 3 Linguagem: Inglês

10.1021/ja010658s

1943-2984

Hideo Tomioka, Tetsuya Watanabe, Makoto Hattori, Naoki Nomura, Katsuyuki Hirai,

Cyclopropane Reaction Mechanisms

A series of polybrominated diphenylcarbenes (DPCs) are generated by irradiation of the corresponding precursor diazomethanes, and their reactivities are investigated by means of low-temperature spectroscopies as well as laser flash photolysis. Triplet bis(2,4,6-tribromophenyl)carbene was shown to decay by undergoing dimerization and to have a half-life of 1 s in a degassed benzene solution at room temperature, some 6 orders of magnitude longer-lived than the parent DPC. Anomalous effects of para substituents on the stability of the triplet are noted. Thus, while the replacement of a 4-bromine group with a methyl group resulted in a sharp decrease in the lifetime, introduction of a tert-butyl group resulted in a dramatic increase in the lifetime; triplet bis(2,6-dibromo-4-tert-butylphenyl)carbene was shown to have a half-life of 16 s in solution at room temperature. Attempts to increase the stability of these polybrominated DPCs by buttressing effects of a m-bromine group and by the synergetic effect of bromine and methyl groups are also described.