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A Platinum(II) Metallonitrene with a Triplet Ground State

preprint
submitted on 03.06.2020 and posted on 04.06.2020 by Sven Schneider, Jian Sun, Josh Abbenseth, Hendrik verplancke, Martin Diefenbach, Bas de Bruin, David Hunger, christian würtele, Joris van Slageren, Max C. Holthausen

Metallonitrenes (M–N) are complexes with a subvalent, atomic nitrogen ligand that have been proposed as key reactive intermediates in nitrogen atom transfer reactions. However, in contrast to the common class of nitride complexes (Mo≡N) and organic nitrenes (R–N), authentic, persistent metallonitrenes remain elusive. We here report that the photolysis of a platinum(II) pincer azide complex enabled the crystallographic, spectroscopic, magnetic and computational characterization of a metallonitrene that is best described as a singly bonded, atomic nitrogen diradical ligand bound to platinum(II). The photoproduct exhibits selective C–H, B–H, and B–C nitrogen atom insertion reactivity. Mechanistic examination of aldehyde C–H amidation surprisingly reveals nucleophilic reactivity of the subvalent N-diradical ligand.

Funding

ERC (Grant Agreement 646747)

DFG (389479699/RTG2455)

DFG (SA1840/7)

DFG (SL104/10)

History

Email Address of Submitting Author

sven.schneider@chemie.uni-goettingen.de

Institution

Universität Göttingen

Country

Germany

ORCID For Submitting Author

0000-0002-8432-7830

Declaration of Conflict of Interest

No conflict of interest to declare.

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