The addition of alkynes HC=CR to Mo(NH)(CH2)(OR')(2) (R = H, Me, Ph; R' = CH3, CF3) has been studied with both ab initio molecular orbital and density functional calculations. Geometry optimizations were carried out with the HF/3-21G, HF/HW3, and B3LYP/HW3 methods. The transition structures for these addition reactions are in distorted trigonal bipyramidal geometries, similar to those of alkene additions. The calculated activation enthalpy for HC=CH addition to Mo(NH)(CH2)(OR')(2) is about 10.3 kcal/mol for R' = CH3 and about 2.3 kcal/mol for R' = CF3, indicating a significant preference for acetylene addition to Mo-(NH)(CH2)(OCF3)(2) over Mo(NH)(CH2)(OCH3)(2). These barriers are higher than those of the corresponding ethylene addition by about 2-4 kcal/mol, even though the reaction of acetylene is much more exothermic. The a-addition of HC=CR (R = Me, Ph) is found to be considerably more favorable than the beta -addition to Mo(NH)(CH2)(OR')(2). Interestingly, the a-addition has a lower activation energy, while the beta -addition has a higher activation energy, compared to that of the parent acetylene addition. Thus, a-addition is intrinsically favored over beta -addition by over 4 kcal/mol. This preference is reduced by solvent effect. All these can be explained by a destabilizing interaction between the nonreacting pi -orbital of alkyne and one of the lone pairs on the imido nitrogen. The steric effect of the bulky ligands in the real catalysts is also investigated qualitatively by the PM3 method. These studies give results in good accord with the experimentally observed regioselectivity.