Lau, SamanthaSamanthaLauWhite, AndrewAndrewWhiteCasely, IanIanCaselyCrimmin, MarkMarkCrimmin2019-01-072019-08-022018-12-10Organometallics, 2018, 37 (23), pp.4521-45260276-7333http://hdl.handle.net/10044/1/65394The reaction of [Ru(H)2(N2)2(PCy3)2] (1) with β-diketiminate stabilized hydrides of Al, Zn, and Mg generates a series of new heterobimetallic complexes with either H2 or N2 ligated to the ruthenium center. Changing the main-group fragment of the M·Ru-N2 (M = Al, Zn, Mg) complexes can subtly alter the degree of binding, and therefore activation, of the diatomic ligand, as evidenced by the νN≡N absorptions in the infrared data. Experimental and computational data rationalize this tunable binding; decreasing the electronegativity of the main group in the order Al > Zn > Mg infers greater ionic character of these M·Ru-N2 complexes, and this in turn results in greater destabilization of the frontier molecular orbitals of ruthenium and therefore greater Ru(4d) → π*(N2) back-donation.© 2018 American Chemical SocietyScience & TechnologyPhysical SciencesChemistry, Inorganic & NuclearChemistry, OrganicChemistryBASIS-SETSSIGMA-COMPLEXESHYDROGEN BONDALUMINUMZINCMAGNESIUMELEMENTSMETALPSEUDOPOTENTIALSCOORDINATION0302 Inorganic Chemistry0305 Organic Chemistry0399 Other Chemical SciencesOrganic ChemistryJournal Articlehttps://www.dx.doi.org/10.1021/acs.organomet.8b00340UF090149