Mechanisms of H-H Insertion and Addition of Cumulene Carbene H2CCC:

Abstract

Abstract: Reactions H₂CCC: (1)+H₂→CH₂CCH₂(2)+CH₃CCH(3) are studied using HF/3-21Ggradient method. The insertion ¹⁺H₂→2 occurs easily in fashion of "end-on" approach with a barrier of about 45 kJ/mol. The addition 1+H₂→3 is fulfilled in two steps, the 2+2 addition toethenylenene carbene, then followed by 1,2-hydrogen migration. Because of the symmetry prohibition, the 2+2 addition proceeds via a 3-center transition state with a high barrier, the 4-center interaction occurs in the later stage. The reactions 1+H₂are kinetically controlled with 2 as the major product. The requirements for the carbene addition are discussed.

Key words: H-H Insertion, "End-on", approach, 2+2 addition, 3-Center transition state

TrendMD:

Wang Bing-ze, Wang Chen-Jian, Deng Cong-hao. Mechanisms of H-H Insertion and Addition of Cumulene Carbene H₂CCC:[J]. Chem. J. Chinese Universities, 1991, 12(5): 644.

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Mechanisms of H-H Insertion and Addition of Cumulene Carbene H₂CCC:

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