Statistical techniques constitute useful approaches to investigate atom-diatom reactions mediated by insertion dynamics which involves complex-forming mechanisms. Different capture schemes based on energy considerations regarding the specific diatom rovibrational states are suggested to evaluate the corresponding probabilities of formation of such collision species between reactants and products in an attempt to test reliable alternatives for computationally demanding processes.These approximations are tested in combination with a statistical quantum mechanical method for the S+H 2 (v = 0, j = 1) → SH+H and Si+O 2 (v = 0, j = 1) → SiO+O reactions, where this dynamical mechanism plays a significant role, in order to probe their validity.