This Letter examines the enthalpy of formation for 12 transition metal diatomic molecules and 23 transition metal complexes from the viewpoint of effect of the relativistic effect by using the infinite-order Douglas-Kroll-Hess method with the local unitary transformation and three types of pseudopotentials for several levels of theory. The spin-orbit effect contribution to the enthalpy of formation is more than 10 kcal/mol for third transition metal complexes. Frozen orbital approximation at the outermost orbitals in pseudopotential methods shows a contribution to the enthalpy of formation that is more than two times larger than those of inner core orbitals. (C) 2017 Elsevier B.V. All rights reserved.