Department of Chemistry, University of Utah, 314 S. 1400 E., Rm 2020, Salt Lake City, Utah, 84112, USA.
J Phys Chem A. 2009 Oct 15;113(41):10955-65. doi: 10.1021/jp907253r.
The gas-phase reactivity of the atomic transition-metal cation rhodium, Rh(+), with CS(2) is investigated using guided-ion-beam mass spectrometry (GIBMS). Endothermic reactions forming RhS(+) and RhCS(+) are observed. Analysis of the kinetic energy dependence of the cross sections for formation of these two products yields the 0 K bond energies of D(0)(Rh(+)-S) = 2.61 +/- 0.12 eV and D(0)(Rh(+)-CS) = 2.66 +/- 0.19 eV. These compare favorably with quantum chemical calculations at the CCSD(T)/Def2TZVPP//B3LYP/Def2TZVPP and CCSD(T)/Def2TZVPP levels of theory, where the former is also used to explore the complete potential energy surface of the reaction. It is found that the reaction initially involves insertion of the rhodium cation into one of the CS bonds of CS(2), followed by metal ligand cleavages to form the two product channels. The formation of ground state RhS(+) products is spin-forbidden, whereas RhCS(+) formation is spin-allowed. Crossing points between the triplet and quintet surfaces are located in the region of the SRh(+)(CS) intermediate, which suggests that coupling between the surfaces is reasonably efficient, consistent with experiment.
采用离子阱质谱（GIBMS）研究了原子过渡金属阳离子铑（Rh(+）与 CS(2）的气相反应性。观察到形成 RhS(+)和 RhCS(+)的吸热反应。分析这两种产物形成的截面的动能依赖性，得出这两个产物的 0 K 键能 D(0)(Rh(+)-S) = 2.61 ± 0.12 eV 和 D(0)(Rh(+)-CS) = 2.66 ± 0.19 eV。这些与 CCSD(T)/Def2TZVPP//B3LYP/Def2TZVPP 和 CCSD(T)/Def2TZVPP 理论水平的量子化学计算结果相当，前者还用于探索反应的完整势能面。发现反应最初涉及铑阳离子插入 CS(2）的 CS 键之一，然后发生金属配体断裂，形成两个产物通道。基态 RhS(+)产物的形成是自旋禁阻的，而 RhCS(+)的形成是自旋允许的。三重态和五重态表面之间的交点位于 SRh(+)(CS）中间体的区域，这表明表面之间的耦合相当有效，与实验结果一致。
