Rh2(II,III) Catalysts with Chelating Carboxylate and Carboxamidate Supports: Electronic Structure and Nitrene Transfer Reactivity

Journal of the American Chemical Society
Adrián Varela-ÁlvarezDjamaladdin G Musaev

Abstract

Dirhodium-catalyzed C-H amination is hypothesized to proceed via Rh2-nitrene intermediates in either the Rh2(II,II) or Rh2(II,III) redox state. Herein, we report joint theoretical and experimental studies of the ground electronic state (GES), redox potentials, and C-H amination of [Rh2(II,III)(O2CCH3)4(L)n](+) (1_L) (L = none, Cl(-), and H2O), [Rh2(esp)2](+) (2), and Rh2(espn)2Cl (3) (esp = α,α,α',α'-tetramethyl-1,3-benzenedipropanoate and espn = α,α,α',α'-tetramethyl-1,3-benzenedipropanamidate). CASSCF calculations on 1_L yield a wave function with two closely weighted configurations, (δ*)(2)(π1*)(2)(π2*)(1) and (δ*)(2)(π1*)(1)(π2*)(2), consistent with reported EPR g values [Chem. Phys. Lett. 1986, 130, 20-23]. In contrast, EPR spectra of 2 show g values consistent with the DFT-computed (π*)(4)(δ*)(1) GES. EPR spectra and Cl K-edge XAS for 3 are consistent with a (π*)(4)(δ*)(1) GES, as supported by DFT. Nitrene intermediates 2N_L and 3N_L are also examined by DFT (the nitrene is an NSO3R species). DFT calculations suggest a doublet GES for 2N_L and a quartet GES for 3N_L. CASSCF calculations describe the GES of 2N as Rh2(II,II) with a coordinated nitrene radical cation, (π*)(4)(δ*)(2)(π(nitrene,1))(1)(π(nitrene,2))(0). Convers...Continue Reading

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Citations

Oct 14, 2016·Journal of the American Chemical Society·Benjamin W NoffkeLiang-Shi Li
Oct 12, 2016·Journal of the American Chemical Society·Nicholas S DolanJennifer M Schomaker
Jan 5, 2017·Chemical Reviews·Yoonsu ParkSukbok Chang
Apr 21, 2017·Chemical Society Reviews·Marcus W DroverLaurel L Schafer
Apr 30, 2017·Chemistry : a European Journal·Ian G PowersChristopher Uyeda
Feb 28, 2018·Angewandte Chemie·Nicholas D ChiappiniJ Du Bois
May 24, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Conrad A P GoodwinStephen Sproules
Sep 20, 2018·Organic & Biomolecular Chemistry·Motoki ItoShigeo Sugiyama
Dec 19, 2018·Chemistry : a European Journal·Masato KonoTetsuhiro Nemoto
Jul 5, 2017·Chemistry : a European Journal·Petrus F KuijpersBas de Bruin
Aug 13, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Juping WangLi Qian
Aug 27, 2019·Journal of the American Chemical Society·Hoimin JungSukbok Chang
Aug 2, 2018·Journal of the American Chemical Society·Anuvab DasDavid C Powers
Nov 2, 2017·Journal of the American Chemical Society·Minxue HuangJennifer M Schomaker
Jun 13, 2019·Journal of the American Chemical Society·Jin-Sheng YuMasakatsu Shibasaki
Aug 9, 2017·Accounts of Chemical Research·Juliet M AldersonJennifer M Schomaker
Jan 5, 2021·Journal of the American Chemical Society·Yuyang DongTheodore A Betley
Sep 25, 2019·Journal of the American Chemical Society·Anuvab DasDavid C Powers
Jun 27, 2020·Organic Process Research & Development·Elisa Martínez-CastroAbraham Mendoza
Oct 6, 2017·ACS Central Science·Huw M L Davies, Daniel Morton

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