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

Nance, Patricia J. and Thompson, Niklas B. and Oyala, Paul H. and Peters, Jonas C. (2019) Zerovalent Rhodium and Iridium Silatranes Featuring Two-Center, Three-Electron Polar σ Bonds. Angewandte Chemie International Edition, 58 (19). pp. 6220-6224. ISSN 1433-7851. http://resolver.caltech.edu/CaltechAUTHORS:20190214-111511215

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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”.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.201814206DOIArticle
ORCID:
AuthorORCID
Nance, Patricia J.0000-0001-7645-0612
Thompson, Niklas B.0000-0003-2745-4945
Oyala, Paul H.0000-0002-8761-4667
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Zerovalent Rh and Ir Silatranes Featuring 2-center, 3-electron Polar Sigma 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.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)0235032
NSFCHE-1531940
Dow Next Generation Educator FundUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Subject Keywords:electronic structure; iridium; metalloradicals; rhodium; structure elucidation
Record Number:CaltechAUTHORS:20190214-111511215
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190214-111511215
Official Citation:P. J. Nance, N. B. Thompson, P. H. Oyala, J. C. Peters, Angew. Chem. Int. Ed. 2019, 58, 6220; doi: 10.1002/anie.201814206
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92936
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Feb 2019 19:28
Last Modified:01 May 2019 20:49

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