Atomization energies were calculated using explicitly correlated coupled cluster methods with correlation consistent basis sets for a series of 19 small molecules containing 3d transition metal atoms. The atomization energies were calculated using a modified Feller-Peterson-Dixon approach in which CCSD(T) complete basis set (CBS) limits were obtained using extrapolations of aVTZ∕aVQZ CCSD(T)-F12b correlation energies, and then a series of additive contributions for relativity, core correlation, higher order correlation, and zero-point vibrations were included. The frozen-core CBS limits calculated with F12 methods closely matched the more computational expensive conventional awCVQZ∕awCV5Z CBS extrapolations, with a mean unsigned deviation of just 0.1 kcal∕mol. In particular, the CCSD(T∗)-F12b∕aVDZ and aVTZ atomization energies were more accurate on average than the conventional CCSD(T)∕aVQZ and aV5Z results, respectively. In several cases the effects of higher order correlation beyond CCSD(T), as judged by CCSDT and CCSDT(Q)Λ calculations, were greater than 1 kcal∕mol, reaching 4.5 kcal∕mol for CrO3. For the 16 molecules of this study with experimental uncertainties of ∼3.5 kcal∕mol or less, the final composite heats of formation have a mean unsigned deviation (MUD) from experiment of just 1.3 kcal∕mol, which is slightly smaller than the average of the experimental uncertainties, 1.8 kcal∕mol. The root mean square deviation (RMS) is only slightly larger at 1.7 kcal∕mol. Without the contributions due to higher order correlation effects, the MUD and RMS rise to 2.1 and 2.8 kcal∕mol, respectively. To facilitate the F12 calculations, new (aug-)cc-pVnZ∕MP2Fit (n = Q, 5) and (aug-)cc-pwCVTZ∕MP2Fit auxiliary basis sets were also developed for the transition metal atoms.