The effect of a bulky phenyl substituent on the formation and stability of pivalate complexes of 3d transition metals is studied on the example of 2-phenylpyridine (phpy). Quantum chemical calculations in the B3LYP/Def2-TZVP approximation are used to optimize binuclear molecules of [M2(μ-piv)4L2] complexes, where M = Co, Ni, Cu, $$\text{piv} = \text{Me}_3\text{CCO}^-_2$$ , L = 2,3-lutidine (lut) for which the analyzed compounds are known, phpy, and 7,8-benzoquinoline (bquin). The calculated energy characteristics indicate a significant stability of lut complexes and suggest that similar compounds with phpy can be prepared. The accuracy of theoretical calculations is confirmed by the successful synthesis of complex [Cu2(piv)4(phpy)2] (3). The computational simulation of binuclear coordination compounds with bquin suggests that there is a theoretical possibility of their formation; however, the fact that such structures have lower stabilization energies than those of reference complexes ([M2(piv)4(DMF)2]) indicates that their preparative isolation is hindered. Molecular structures of novel molecular complexes [Ni9(OH)6(piv)12(Hpiv)2(phpy)]·C6H6 (2) and [Li2Co2(piv)6(phpy)2] (4) are isolated and determined.