Zerovalent Rhodium and Iridium Silatranes Featuring Two-Center, Three-Electron Polar σ Bonds
Abstract
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".
Additional Information
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Version of Record online: 01 April 2019; Accepted manuscript online: 13 February 2019; Manuscript revised: 26 January 2019; Manuscript received: 13 December 2018. We are grateful for funding from the Department of Energy (DOE‐0235032), from the NSF through its MRI program (NSF‐1531940) in support of the Caltech EPR facility, and to the DOW Next Generation Educator Fund. PJN is grateful for an NSF GRF. We also thank Dr. Michael Takase and Larry Henling for assistance with X‐ray crystallography. The authors declare no conflict of interest.Attached Files
Supplemental Material - anie201814206-s1-supporting_information_pjn.pdf
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Additional details
- Alternative title
- Zerovalent Rh and Ir Silatranes Featuring 2-center, 3-electron Polar Sigma Bonds
- Eprint ID
- 92936
- Resolver ID
- CaltechAUTHORS:20190214-111511215
- Department of Energy (DOE)
- 0235032
- NSF
- CHE-1531940
- Dow Next Generation Educator Fund
- NSF Graduate Research Fellowship
- Created
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2019-02-14Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field