Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C₅Me₅)ZnH and (C₅Me₅)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex

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 Mo atoms dimolybdenum quadruple Mo–Mo bonds. addition, reactivity bis(hydride) [Mo2(H)2(μ-AdDipp2)2(thf)2] complex (AdDipp2 HC[N(2,6-iPr2C6H3)]2) with zincocenes Zn(C5Me5)2 and Zn2(η5-C5Me5)2 reveals formation compounds which (C5Me5)Zn–H (C5Me5)ZnZn–H bind trans-H–Mo≣Mo–H core. DFT calculations an NBO analysis disclose a general bonding mechanism reported H–Mo≣Mo–E–R rings that is consistent penetration indices different atom pairs. The comprises three center–two electron Mo–H–E Mo–R–E supplemented by π-coordination Mo≣Mo bond electropositive E.