Zerovalent Rhodium and Iridium Silatranes Featuring Two‐Center, Three‐Electron Polar σ Bonds
| Autor: | Jonas C. Peters, Patricia J. Nance, Paul H. Oyala, Niklas B. Thompson |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Materials science
010405 organic chemistry Ligand chemistry.chemical_element Trigonal pyramidal molecular geometry General Chemistry Electronic structure General Medicine 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Rhodium law.invention Crystallography chemistry Atomic orbital law Reactivity (chemistry) Iridium Electron paramagnetic resonance |
| Zdroj: | Angewandte Chemie. 131:6286-6290 |
| ISSN: | 1521-3757 0044-8249 |
| DOI: | 10.1002/ange.201814206 |
| Popis: | 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 (d^9) 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”. |
| Databáze: | OpenAIRE |
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