Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents
Abstract
Recent research has highlighted the key role played by the electron affinity of the active metal-nitrene/imido oxidant as the driving force in nitrene additions to olefins to afford valuable aziridines. The present work showcases a library of Co(II) reagents that, unlike the previously examined Mn(II) and Fe(II) analogues, demonstrate reactivity trends in olefin aziridinations that cannot be solely explained by the electron affinity criterion. A family of Co(II) catalysts (17 members) has been synthesized with the assistance of a trisphenylamido-amine scaffold decorated by various alkyl, aryl, and acyl groups attached to the equatorial amidos. Single-crystal X-ray diffraction analysis, cyclic voltammetry and EPR data reveal that the high-spin Co(II) sites (S = 3/2) feature a minimal [N3N] coordination and span a range of 1.4 V in redox potentials. Surprisingly, the Co(II)-mediated aziridination of styrene demonstrates reactivity patterns that deviate from those anticipated by the relevant electrophilicities of the putative metal nitrenes. The representative L4Co catalyst (-COCMe3 arm) is operating faster than the L8Co analogue (-COCF3 arm), in spite of diminished metal-nitrene electrophilicity. Mechanistic data (Hammett plots, KIE, stereocontrol studies) reveal that although both reagents follow a two-step reactivity path (turnover-limiting metal-nitrene addition to the Cb atom of styrene, followed by product-determining ring-closure), the L4Co catalyst is associated with lower energy barriers in both steps. DFT calculations indicate that the putative [L4Co]NTs and [L8Co]NTs species are electronically distinct, inasmuch as the former exhibits a single-electron oxidized ligand arm. In addition, DFT calculations suggest that including London dispersion corrections for L4Co (due to the polarizability of the tert-Bu substituent) can provide significant stabilization of the turnover-limiting transition state. This study highlights how small ligand modifications can generate stereoelectronic variants that in certain cases are even capable of overriding the preponderance of the metal-nitrene electrophilicity as a driving force.
Recommended Citation
A. Kalra and V. Bagchi and P. Paraskevopoulou and P. Das and L. Ai and Y. Sanakis and G. Raptopoulos and S. Mohapatra and A. Choudhury and Z. Sun and T. R. Cundari and P. Stavropoulos, "Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents," Organometallics, vol. 40, no. 12, pp. 1974 - 1996, American Chemical Society (ACS), Jun 2021.
The definitive version is available at https://doi.org/10.1021/acs.organomet.1c00267
Department(s)
Chemistry
International Standard Serial Number (ISSN)
0276-7333; 1520-6041
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2021 American Chemical Society (ACS), All rights reserved.
Publication Date
04 Jun 2021
Comments
This work was generously supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Numbers R15GM117508 and R15GM139071 (to P.S.), and in part by the National Science Foundation through grant CHE-0412959 (to P.S.).