Providing tools to understand the physical mechanisms governing magnetic properties in transition metal-based compounds is still of great interest. Here, the magnetic exchange coupling in a series of heterodinuclear complexes is investigated by means of the decomposition method. This work presents the first application of the decomposition method to systems where magnetic centres may bear more than one unpaired electron. By decomposing the coupling into three physical contributions (direct exchange, kinetic exchange, and spin polarisation), we provide numerical arguments to confirm or infirm the rationalisation allowed by the conceptual analysis of the magnetic d orbitals. We also take advantage of the recently proposed generalisation of the method [David et al., J. Chem. Theory Comput., 2023, 19, 157] to get more insights into the underlying mechanisms by disentangling the coupling between centres into its electron-electron interactions.