Zerovalent Rhodium and Iridium Silatranes Featuring Two-Center, Three-Electron Polar σ Bonds

Species with 2-center, 3-electron (2c/3e^- ) σ bonds are of interest owing to their fascinating electronic structures and potential for interesting reactivity patterns. Report here is the synthesis and characterization of a pair of zerovalent (d⁹ ) trigonal pyramidal Rh and Ir complexes that feature 2c/3e^- σ bonds to the Si atom of a tripodal tris(phosphine)silatrane ligand. X-ray diffraction, continuous wave and pulse electron paramagnetic resonance, density-functional theory calculations, and reactivity studies have been used to characterize these electronically distinctive compounds. The data available highlight a 2c/3e^- bonding framework with a σ*-SOMO of metal 4- or 5d_z ² parentage that is partially stabilized by significant mixing with Si (3p_z ) and metal (5- or 6p_z ) orbitals. Metal-ligand covalency thus buffers the expected destabilization of transition-metal (TM)-silyl σ*-orbitals by d-p mixing, affording well-characterized examples of TM-main group, and hence polar, 2c/3e^- σ "half-bonds".