Striking relativistic effects are demonstrated for the ligation of carbon disulphide to late atomic transition metal cations (Groups 9-11) with both measurements of rate coefficients for ligation in helium buffer gas at 0.35 ± 0.01 Torr and 295 ± 2 K and quantum chemical calculations of ligation energies. The rates of ligation with one CS₂ molecule were observed to be enhanced by a factor of about 10 going from second row to third-row atomic transition metal cations (Groups 9-11). The addition of a second CS₂ ligand, although intrinsically much faster due to effects of degrees of freedom on the lifetime of the intermediate, also exhibits enhancement of the ligation rate for the third-row atomic cations for Groups 10 and 11. The trends in the computed M⁺-CS₂ bond dissociation energies down Groups 9-11clearly follow the trends in the measured rate coefficients for the first addition of CS₂ and, to a degree, the second addition. A novel isodesmic reaction method was used to estimate the percent relativistic contribution to the M⁺-CS₂ bond energy down the periodic table which exceeds 25% for third-row atomic ions. The computations also provided optimized structures for the ligated ions M⁺(CS₂) and M⁺(CS₂)₂. A correlation between the measured ligation efficiency and the computed ligation energy provided a measure of the number of vibrational modes active in the stabilization of these ligated ions.

证明了二硫化碳与晚期原子过渡金属阳离子（9-11族）的连接具有惊人的相对论效应，在氦缓冲气体中以0.35±0.01 Torr和295±2 K的速率测定了连接速率系数，并进行了量子化学计算。结扎能量。从第二行到第三行原子过渡金属阳离子，观察到与一个CS ₂分子的连接速率提高了约10倍（第9-11组）。尽管由于自由度对中间体寿命的影响，第二种CS ₂配体的加入虽然本来就快得多，但也显示出第10和11组第三行原子阳离子的连接速率提高。计算的M ⁺ -CS₂键解离能下降第9-11组清楚地遵循了第一次添加CS ₂以及一定程度上第二次添加时测得的速率系数的趋势。一种新颖的等渗反应方法被用来估算相对于元素周期表中M ⁺ -CS ₂键能的相对论贡献百分比，对于第三行原子离子，其超过25％。计算还为连接离子M ⁺（CS ₂）和M ⁺（CS ₂）₂提供了优化的结构。测得的连接效率与计算的连接能量之间的相关性提供了对稳定这些连接离子的振动模式数量的度量。