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

Nance, Patricia J.; Thompson, Niklas B.; Oyala, Paul H.; Peters, Jonas C.

doi:10.1002/anie.201814206

Title: Zerovalent Rhodium and Iridium Silatranes Featuring Two–Center, Three–Electron Polar σ Bonds

Journal Article · 13 February 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201814206 · OSTI ID:1707744

Nance, Patricia J. ^[1]; Thompson, Niklas B. ^[2];

^[2];

^[2]

California Institute of Technology (CalTech), Pasadena, CA (United States); California Institute Technology
California Institute of Technology (CalTech), Pasadena, CA (United States)

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. Here, the data available highlight a 2c/3e^– bonding framework with a σ*–SOMO of metal 4– or 5d_z² 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”.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0019136

OSTI ID:: 1707744

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 19 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (4)

Three‐Coordinate Rhodium Complexes in Low Oxidation States Varela‐Izquierdo, Víctor; López, José A.; Bruin, Bas Chemistry – A European Journal, Vol. 26, Issue 15 https://doi.org/10.1002/chem.202000387	journal	March 2020
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Iridium complexes featuring a tridentate SiPSi ligand: from dimeric to monomeric 14, 16 or 18-electron species Cuevas-Chávez, Cynthia A.; Vendier, Laure; Sabo-Etienne, Sylviane Dalton Transactions, Vol. 48, Issue 37 https://doi.org/10.1039/c9dt03136g	journal	January 2019
Tunable carbocation-based redox active ambiphilic ligands: synthesis, coordination and characterization Mei, Liangyong; Veleta, José M.; Bloch, Jan Dalton Transactions https://doi.org/10.1039/d0dt00419g	journal	January 2020

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CCDC 1884358: Experimental Crystal Structure Determination Nance, Patricia J.; Thompson, Niklas B.; Oyala, Paul H. https://doi.org/10.5517/ccdc.csd.cc217trw The current record is supplemented by this dataset	dataset	January 2019
CCDC 1884359: Experimental Crystal Structure Determination Nance, Patricia J.; Thompson, Niklas B.; Oyala, Paul H. https://doi.org/10.5517/ccdc.csd.cc217tsx The current record is supplemented by this dataset	dataset	January 2019
CCDC 1884360: Experimental Crystal Structure Determination Nance, Patricia J.; Thompson, Niklas B.; Oyala, Paul H. https://doi.org/10.5517/ccdc.csd.cc217tty The current record is supplemented by this dataset	dataset	January 2019