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Palladium Terminal Imido Complexes with Nitrene Character



Grünwald, Annette;

Goswami, Bhupendra;

Breitwieser, Kevin;

Morgenstern, Bernd;

Gimferrer, Martí;

Heinemann, Frank W;

Momper, Dajana M;

Munz, Dominik; + view all

Grünwald, Annette;

Goswami, Bhupendra;

Breitwieser, Kevin;

Morgenstern, Bernd;

Gimferrer, Martí;

Heinemann, Frank W;

Momper, Dajana M;

Kay, Christopher WM;

Munz, Dominik;

– view fewer

(2022)

Palladium Terminal Imido Complexes with Nitrene Character.

Journal of the American Chemical Society
, 144
(20)

pp. 8897-8901.

10.1021/jacs.2c02818.


Text

manuscript.pdf
– Accepted Version

Access restricted to UCL open access staff until 26 May 2023.

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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.

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