Described herein is a comparative theoretical study of dehydrogenative C(sp)-H functionalizations of a terminal alkyne with group-14-based hydrides (HEEt3; E = Si, Ge, Sn) catalyzed by an Ohki-Tatsumi complex - a cationic Ru(II) complex with a tethered thiolate ligand ([Ru-S] = [(DmpS)Ru(PiPr3)][BAr4F]; Dmp = 2,6-(dimesityl)2C6H3; ArF = 3,5-(CF3)2C6H3). The calculations indicate that the energy barriers for heterolytic cleavage of the H-EEt3 bonds at the Ru-S sites of the Ohki-Tatsumi complex highly vary depending on the group 14 elements from 3.8 kcal/mol (E = Sn) to 10.5 kcal/mol (E = Ge) and 18.5 kcal/mol (E = Si), where Ru and S elements cooperatively serve as the Lewis acid and base, respectively. Likewise, the transfer of the group 14 cation (Et3E+) to the C-C triple bond to generate the β-element-stabilized vinyl cations - the rate-determining step (RDS) of the overall reaction - is predicted to be susceptible to the element's identity [Ea = 36.8 for Sn < 42.9 and Ge < 50.7 for Si (kcal/mol)]. The key transition states involved in the RDS are compared in terms of energy and structure within each system of the group 14 hydrides. The distortion/interaction-activation strain (DIAS) model analysis of the transition states responsible for dehydrogenative stannylation and hydrostannation of a terminal alkyne sheds light on the origin of the experimentally observed kinetic preference toward dehydrogenative C-H stannylation over hydrostannation.