Molybdenum(VI) bis-imido Complexes of Dipyrromethene Ligands

Locher J, Watt FA, Neuba AG, Schoch R, Munz D, Hohloch S (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Inorganic Chemistry American Chemical Society

DOI: 10.1021/acs.inorgchem.0c01051

Abstract

We report the synthesis of high-valent molybdenum(VI) bis-imido complexes 1-4 with dipyrromethene (DPM) supporting ligands of the general formula (DPMR)Mo(NR′)2Cl (R, R′ = mesityl (Mes) or tert-butyl (tBu)). The electrochemical and chemical properties of 1-4 reveal unexpected ligand noninnocence and reactivity. 15N NMR spectroscopy is used to assess the electronic properties of the imido ligands in the tert-butyl complexes 1 and 3. Complex 1 is inert toward ligand (halide) exchange with bulky phenolates such as KOMes or amides (e.g., KN(SiMe3)2), whereas the use of the lithium alkyl LiCH2SiMe3 results in a rare nucleophilic β-alkylation of the DPM ligand. While the reductions of the complexes occur at molybdenum, the oxidation is centered at the DPM ligand. Quantum-chemical calculations (complete active space self-consistent field, density functional theory) suggest facile (near-infrared) interligand charge transfer to the imido ligand, which might preclude the isolation of the oxidized complex [1]+ in the experiment.

Authors with CRIS profile

Dominik Munz Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universität Paderborn DE Germany (DE) Leopold-Franzens-Universität Innsbruck / University of Innsbruck AT Austria (AT)

How to cite

APA:

Locher, J., Watt, F.A., Neuba, A.G., Schoch, R., Munz, D., & Hohloch, S. (2020). Molybdenum(VI) bis-imido Complexes of Dipyrromethene Ligands. Inorganic Chemistry. https://dx.doi.org/10.1021/acs.inorgchem.0c01051

MLA:

Locher, Jan, et al. "Molybdenum(VI) bis-imido Complexes of Dipyrromethene Ligands." Inorganic Chemistry (2020).

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