Sengupta Turbasu, Khan Muntazir S, Pal Sourav
Physical Chemistry Division, CSIR National Chemical Laboratory, Pune 411008, India.
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
ACS Omega. 2017 Sep 1;2(9):5335-5347. doi: 10.1021/acsomega.7b00894. eCollection 2017 Sep 30.
The activation process of carbon-iodine (C-I) bond on neutral and cationic niobium metcars (NbC) is investigated using density functional theory and related computational techniques. Metallocarbohedrenes or metcars are a class of stable metal-carbide clusters of specific stoichiometry and of great interest to cluster chemists since their first discovery. The detailed reaction mechanism along with the overall energy profile of the C-I dissociation reaction on niobium metcar and its cations is presented in this paper. The tunneling-corrected rate constants and their related reaction parameters such as the pre-exponential factor are also included alongside. The major differences between the reaction mechanism of the neutral and cationic metcars are also highlighted as well. Despite the available experimental results, the C-I bond dissociation on metcars has remained an unexplored problem in the theoretical and computational domains. Thus, the present investigation can fill in the gap and may also provide new insights provoking further developments in cluster and materials chemistry in future.
利用密度泛函理论和相关计算技术，研究了中性和阳离子型金属碳硼烷（NbC）上碳 - 碘（C - I）键的活化过程。金属碳硼烷是一类具有特定化学计量比的稳定金属碳化物簇，自首次发现以来一直受到簇化学家的极大关注。本文给出了在金属碳硼烷及其阳离子上C - I解离反应的详细反应机理以及整体能量分布。同时还包括隧穿校正速率常数及其相关反应参数，如指前因子。中性和阳离子型金属碳硼烷反应机理之间的主要差异也得到了突出显示。尽管已有实验结果，但金属碳硼烷上的C - I键解离在理论和计算领域仍是一个未被探索的问题。因此，本研究可以填补这一空白，也可能提供新的见解，激发未来簇化学和材料化学的进一步发展。
