A platinum(ii) metallonitrene with a triplet ground state
- 24 August 2020
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Chemistry
- Vol. 12 (11), 1054-1059
- https://doi.org/10.1038/s41557-020-0522-4
Abstract
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 classes of nitride complexes (M≡N) and organic nitrenes (R–N), structurally and spectroscopically well defined ‘authentic’ metallonitrenes with a monovalent atomic nitrogen ligand remain elusive. Here we 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. Despite the subvalent metallonitrene character, mechanistic analysis for aldehyde C–H amidation shows nucleophilic reactivity of the N-diradical ligand. Ambiphilic reactivity of the metallonitrene is indicated by reactions with CO and PMe3 to form isocyanate and phosphoraneiminato platinum(ii) complexes, respectively.Keywords
This publication has 55 references indexed in Scilit:
- A Crystalline Singlet Phosphinonitrene: A Nitrogen Atom–Transfer AgentScience, 2012
- Ligand‐Accelerated Activation of Strong C-H Bonds of Alkanes by a (Salen)ruthenium(VI)–Nitrido ComplexAngewandte Chemie, 2012
- Synthesis and Characterization of Three-Coordinate Ni(III)-Imide ComplexesJournal of the American Chemical Society, 2011
- A Two-Coordinate Nickel Imido Complex That Effects C−H AminationJournal of the American Chemical Society, 2010
- Uranium azide photolysis results in C–H bond activation and provides evidence for a terminal uranium nitrideNature Chemistry, 2010
- Activation of Carbon−Hydrogen and Hydrogen−Hydrogen Bonds by Copper−Nitrenes: A Comparison of Density Functional Theory with Single- and Multireference Correlation Consistent Composite ApproachesJournal of Chemical Theory and Computation, 2009
- Catalytic C–H functionalization by metal carbenoid and nitrenoid insertionNature, 2008
- Unprecedented carbon–carbon bond formation induced by photoactivation of a platinum(iv)-diazido complexChemical Communications, 2007
- A survey of Hammett substituent constants and resonance and field parametersChemical Reviews, 1991
- X 3A2, a 1E, and b 1A1 electronic states of methylnitreneJournal of the American Chemical Society, 1974