Heterobimetallic complexes containing M–C–E linkages (M = transition metal atom; E = main group metal) have been postulated as relevant intermediates in cross-coupling reactions. Despite this, structural data for these species are scarce. In this contribution, we explore the coordination of E–C bonds (E = Zn, Mg, Al) to the Mo atoms of dimolybdenum complexes containing quadruple Mo–Mo bonds. In addition, the reactivity of the bis(hydride) [Mo2(H)2(μ-AdDipp2)2(thf)2] complex (AdDipp2 = HC[N(2,6-iPr2C6H3)]2) with the zincocenes Zn(C5Me5)2 and Zn2(η5-C5Me5)2 reveals the formation of dimolybdenum compounds in which (C5Me5)Zn–H and (C5Me5)ZnZn–H bonds bind to the trans-H–Mo≣Mo–H core. DFT calculations and an NBO analysis disclose a general bonding mechanism for the reported H–Mo≣Mo–E–R rings that is consistent with the penetration indices of the different atom pairs. The bonding comprises three center–two electron Mo–H–E and Mo–R–E bonds supplemented by π-coordination of the Mo≣Mo bond to the electropositive metal E.