Palladium Terminal Imido Complexes with Nitrene Character

Grünwald A, Goswami B, Breitwieser K, Morgenstern B, Gimferrer M, Heinemann FW, Momper DM, Kay CW, Munz D (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Journal of the American Chemical Society American Chemical Society

DOI: 10.1021/jacs.2c02818

Abstract

Whereas triplet-nitrene complexes of the late transition metals are isolable and key intermediates in catalysis, singlet-nitrene ligands remain elusive. Herein we communicate three such palladium terminal imido complexes with singlet ground states. UV-vis-NIR electronic spectroscopy with broad bands up to 1400 nm as well as high-level computations (DFT, STEOM-CCSD, CASSCF/NEVPT2, EOS analysis) and reactivity studies suggest significant palladium(0) singlet-nitrene character. Although the aliphatic nitrene complexes proved to be too reactive for isolation in analytically pure form as a result of elimination of isobutylene, the aryl congener could be characterized by SC-XRD, elemental analysis, IR-, NMR spectroscopy, and HRMS. The complexes' distinguished ambiphilicity allows them to activate hexafluorobenzene, triphenylphosphine, and pinacol borane, catalytically dehydrogenate cyclohexene, and aminate ethylene via nitrene transfer at or below room temperature.

Authors with CRIS profile

Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universität des Saarlandes (UdS) DE Germany (DE) Universitat de Girona ES Spain (ES)

How to cite

APA:

Grünwald, A., Goswami, B., Breitwieser, K., Morgenstern, B., Gimferrer, M., Heinemann, F.W.,... Munz, D. (2022). Palladium Terminal Imido Complexes with Nitrene Character. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.2c02818

MLA:

Grünwald, Annette, et al. "Palladium Terminal Imido Complexes with Nitrene Character." Journal of the American Chemical Society (2022).

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