Ground-state properties of ruthenium(II) and osmium(II) tin trihydride complexes: A DFT study

DFT methods have been applied for the calculation of several ground-state properties of neutral and charged ruthenium(II) and osmium(II) tin trihydride complexes bearing N-donor, P-donor and C-donor ancillary ligands in their coordination sphere. Complexes of the type M(SnH3)(Tp)(PPh3)P(OMe)3, M(SnH3)(Cp)(PPh3)P(OMe)3 and [M(SnH3)(Bpy)2P(OMe)3]+ (M = Ru, Os; Tp = tris(pyrazol-1-yl)borate; Cp = cyclopentadienyl ion; Bpy = 2,2′-bipyridine) have been studied using the EDF2 and B3PW91 functionals. The same calculations have been carried out also on the corresponding [M]–CH3 and [M]–H compounds, to compare the electronic features of the different reactive ligands coordinated to the same metal fragments. Charge distribution analyses were used to give insight into the roles of the transition metal centres and the ancillary ligands on the properties of the coordinated SnH3 group. The molecular orbitals of the methyl- and trihydrostannyl-complexes were compared to understand the nature of the [M]–SnH3 bond and the electronic transitions of these species.

Several ground-state properties of neutral and charged ruthenium(II) and osmium(II) tin trihydride complexes bearing N-donor, P-donor and C-donor ancillary ligands in their coordination sphere have been calculated by means of DFT methods. The same calculations have been carried out also on the corresponding [M]–CH3 and [M]–H derivatives for comparison. Charge and density distribution analyses were used to give insight into the roles of the transition metal fragments on the properties of the coordinated SnH3 ligand. The molecular orbitals of the methyl- and trihydrostannyl-complexes were analysed to understand the nature of the [M]–SnH3 bond.Figure optionsDownload as PowerPoint slideHighlights
► The ancillary ligands strongly influence the M–Sn bond in [M]–SnH3.
► [Os]–SnH3 bond is stronger than [Ru]–SnH3.
► Hydrogen atoms in [M]–SnH3 have a strong hydride character.
► M–C in [M]–CH3 is more polarised than M–Sn in [M]–SnH3.
► M–Sn in [M]–SnH3 is a σ-bond.