To understand the metal-metal bonding and conformational flexibility of first-row transition metal heterobimetallic complexes, a series of heterobimetallic Ti/M and V/ M complexes (M = Fe, Co, Ni, and Cu) have been investigated. The titanium tris(phosphinoamide) precursors ClTi(XylNP(i)Pr(2))(3) (1) and Ti(XylNP(i)Pr(2))(3) (2) have been used to synthesize Ti/Fe (3), Ti/Ni (4, 4(THF), and Ti/Cu (5) heterobimetallic complexes. A series of V/M (M = Fe (7), Co (8), Ni (9), and Cu (10)) complexes have been generated starting from the vanadium tris(phosphinoamide) precursor V(XylNP(i)Pr(2))(3) (6). new heterobimetallic complexes were characterized and studied by NMR spectroscopy, X-ray crystallography, electron paramagnetic resonance, spectroscopy, where applicable, and computational methods (DFT). Compounds 3, 4(THF), 7, and 8 are C-3-symmetric with three bridging phosphinoamide ligands, while compounds 9 and 10 adopt an asymmetric geometry with two bridging phospbinoamides and one phosphinoamide ligand bound eta(2) to vanadium. Compounds 4 and 5, on the other hand, are asymmetric in the solid state but show evidence for fluxional behavior in solution. A correlation is established between conformational flexibility and metal-metal bond order, which has important implications for the future reactivity of these and other heterobimetallic molecules.