The temperature- and pressure-dependent kinetics of Co⁺(CH₃Br)_n (n = 0,1) + CH₃Br are measured from 300 to 600 K and from 0.2 to 0.5 Torr. Results are interpreted using density functional calculations and modeled with statistical theory. In the n = 0 case, the associative product Co⁺(CH₃Br) dominates with a rate constant between 5 and 30% of the collisional value, while a minor channel yields CoBr⁺ + CH₃ with a rate constant increasing with temperature. 0K bond dissociation energies (BDE) are determined for Co⁺-Br (2.8 ± 0.1 eV) and Co⁺-CH₃Br (2.4 ± 0.25 eV). Ligation of Co⁺ (i.e. n = 1) significantly increases the bimolecular reaction rate constant. CoBr⁺(CH₃Br) + CH₃ is formed and the reaction has a positive temperature dependence. Interestingly, this rate constant decreases with increasing pressure due to competition of the association channel. Ligation increases the (CH₃Br)Co⁺-Br BDE (3.0 ± 0.1 eV) relative to Co⁺-Br, but decreases the (CH₃Br)Co⁺-CH₃Br BDE (1.95 ± 0.25) relative to Co⁺-CH₃Br. Both bimolecular reactions proceed by a metal-insertion mechanism with a significantly submerged transition state that does not affect the kinetics. Instead, the endothermicity of the reaction is rate-limiting. Discussion about how energy, impact parameter, and angular momentum affect specific rate constants for dissociation to reactants, reaction to products, and association are presented.

Co ⁺ (CH ₃ Br) _n (n = 0,1) + CH ₃ Br的温度和压力相关动力学在300 至 600 K 和 0.2 至 0.5 Torr 范围内测量。使用密度泛函计算解释结果并使用统计理论建模。在 n = 0 的情况下，缔合产物 Co ⁺ (CH ₃ Br) 以碰撞值的 5% 到 30% 之间的速率常数占主导地位，而次要通道产生 CoBr ⁺  + CH ₃，速率常数随温度增加。确定 Co ⁺ -Br (2.8 ± 0.1 eV) 和 Co ⁺ -CH _{3 的}0K 键解离能 (BDE)溴 (2.4 ± 0.25 eV)。Co ⁺ (即n = 1) 的连接显着增加了双分子反应速率常数。形成 CoBr ⁺ (CH ₃ Br) + CH ₃并且反应具有正温度依赖性。有趣的是，由于关联通道的竞争，该速率常数随着压力的增加而降低。连接增加了 (CH ₃ Br)Co ⁺ -Br BDE (3.0 ± 0.1 eV) 相对于 Co ⁺ -Br，但降低了 (CH ₃ Br)Co ⁺ -CH ₃ Br BDE (1.95 ± 0.25) 相对于 Co ⁺ -CH ₃兄弟 两种双分子反应都是通过金属插入机制进行的，具有不影响动力学的显着浸没过渡态。相反，反应的吸热性是限速的。讨论了能量、冲击参数和角动量如何影响分解为反应物、反应为产物和缔合的特定速率常数。