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

• Published in: Angewandte Chemie 2019-05, Vol.131 (19), p.6286-6290
• Main Authors: Nance, Patricia J., Thompson, Niklas B., Oyala, Paul H., Peters, Jonas C.
• Format: Article
• Language: English
• Subjects: Chemistry; Continuous radiation; Covalent bonds; Destabilization; Electron paramagnetic resonance; Electrons; Elektronenstruktur; Iridium; Ligands; Metalloradikale; Metals; Orbitals; Partial stabilization; Phosphine; Rhodium; Strukturaufklärung; Wave diffraction; X-ray diffraction
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201814206

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 5dz2 parentage that is partially stabilized by significant mixing with Si (3pz) and metal (5‐ or 6pz) 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”. Halbe‐halbe: Nullwertige (d9) trigonal‐pyramidale Rh‐ und Ir‐Silatrane mit 2c/3e‐σ‐Bindungen wurden hergestellt. Spektroskopische und theoretische Daten zeigen, dass Metall‐Ligand‐Kovalenz die erwartete Destabilisierung ihrer Übergangsmetall(TM)‐Silyl‐σ*‐Orbitale durch d‐p‐Vermischung puffert; es handelt sich somit um Beispiele polarer TM‐Hauptgruppen‐2c/3e‐σ‐„Halbbindungen”.