isolating-free-carbenes-their-mixed-dimers-and-organic-radicals

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Protocols for the isolation of the commonly employed cyclic (alkyl)(amino) carbene (CAAC) and N-heterocyclic carbene (NHC) are reported. Furthermore, the ...

Friedrich-Alexander-Universität Erlangen-Nürnberg

The isolation of terminal oxo complexes of the late transition metals promises new avenues in oxidation catalysis like the selective and catalytic hydroxylation of unreactive CH bonds, the activation of water, or the upgrading of olefins. While terminal oxo ligands are ubiquitous for early transition metals, well-characterized examples with group 10 metals remain hitherto elusive. In search for palladium terminal oxo complexes, the relative stability/reactivity of such compounds are evaluated computationally (CASSCF/NEVPT2; DFT). The calculations investigate only well-known ligand systems with established synthetic procedures and relevance for coordination chemistry and homogeneous catalysis. They delineate and quantify, which electronic properties of ancillary ligands are crucial for taming otherwise highly reactive terminal oxo intermediates. Notably, carbene ligands with both strong σ-donor and strong π-acceptor properties are best suited for the stabilization of palladium(ii) terminal oxo complexes, whereas ligands with a weaker ligand field lead to highly reactive complexes. Strongly donating ligands are an excellent choice for high-valent palladium(iv) terminal oxo compounds. Low coordinate palladium(ii) as well as high-valent palladium(iv) complexes are best suited for the activation of strong bonds.

How to tame a palladium terminal oxo.

Organic singlet diradicaloids promise application in non-linear optics, electronic devices and singlet fission. The stabilization of carbon allotropes/cumulenes (C, C, C) by carbenes has been equally an area of high activity. Combining these fields, we showed recently that carbene scaffolds allow as well for the design of diradicaloids. Herein, we report a comprehensive computational investigation (CASSCF/NEVPT2; fractional occupation DFT) on the electronic properties of carbene-bridge-carbene type diradicaloids. We delineate how to adjust the properties of these ensembles through the choice of carbene and bridge and show that already a short C bridge results in remarkable diradicaloid character. The choice of the carbene separately tunes the energies of the S and T excited states, whereas the bridge adjusts the overall energy level of the excited states. Accordingly, we develop guidelines on how to tailor the electronic properties of these molecules. Of particular note, fractional occupation DFT is an excellent tool to predict singlet-triplet gaps.

Carbene derived diradicaloids - building blocks for singlet fission?

Herein, we report the isolation and a reactivity study of the first example of an elusive palladium(II) terminal imido complex. This scaffold is an alleged key intermediate for various catalytic processes, including the amination of C-H bonds. We demonstrate facile nitrene transfer with H-H, C-H, N-H, and O-H bonds and elucidate its role in catalysis. The high reactivity is due to the population of the antibonding highest occupied molecular orbital (HOMO), which results in unique charge separation within the closed-shell imido functionality. Hence, N atom transfer is not necessarily associated with the high valency of the metal (Pd , Pd ) or the open-shell character of a nitrene as commonly inferred.

Article	Year
How to tame a palladium terminal oxo. Chemical science\| PubMed ID: 29675160	2018
Carbene derived diradicaloids - building blocks for singlet fission? Chemical science\| PubMed ID: 30090299	2018
An Isolable Terminal Imido Complex of Palladium and Catalytic Implications. Angewandte Chemie (International ed. in English)\| PubMed ID: 30312511	2018

Dominik Munz

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