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Zerovalent Rhodium and Iridium Silatranes Featuring Two‐Center, Three‐Electron Polar σ Bonds
Author(s) -
Nance Patricia J.,
Thompson Niklas B.,
Oyala Paul H.,
Peters Jonas C.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201814206
Subject(s) - reactivity (psychology) , chemistry , rhodium , iridium , crystallography , ligand (biochemistry) , atomic orbital , molecular orbital , trigonal pyramidal molecular geometry , density functional theory , phosphine , electron paramagnetic resonance , computational chemistry , molecule , electron , crystal structure , catalysis , nuclear magnetic resonance , organic chemistry , medicine , biochemistry , physics , alternative medicine , receptor , pathology , quantum mechanics
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”.