A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d(7)-Mn(CO)(5) radical

Kalra S, Pividori DM, Fehn D, Dai C, Dong S, Yao S, Zhu J, Meyer K, Driess M (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Chemical Science Royal Society of Chemistry

DOI: 10.1039/d2sc03352f

Abstract

Using the potentially tridentate N,N'-bis(N-heterocyclic silylene)pyridine [SiNSi] pincer-type ligand, 2,6-N,N'-diethyl-bis[N,N'-di-tert-butyl(phenylamidinato)silylene] diaminopyridine, led to the first isolable bis(silylene)pyridine-stabilized manganese(0) complex, {kappa(3)-[SiNSi]Mn(dmpe)} 4 (dmpe = (Me2P)(2)C2H4), which represents an isolobal 17 VE analogue of the elusive Mn(CO)(5) radical. The compound is accessible through the reductive dehalogenation of the corresponding dihalido (SiNSi)Mn(II) complexes 1 (Cl) and 2 (Br) with potassium graphite. Exposing 4 towards the stronger pi-acceptor ligands CO and 2,6-dimethylphenyl isocyanide afforded the related Mn(0) complexes kappa(2)-[SiNSi]Mn(CO)(3) (5) and kappa(3)-[SiNSi] Mn(CNXylyl)(2)(kappa(1)-dmpe) (6), respectively. Remarkably, the stabilization of Mn(0) in the coordination sphere of the [SiNSi] ligand favors the d(7) low-spin electronic configuration, as suggested by EPR spectroscopy, SQUID measurements and DFT calculations. The suitability of 4 acting as a superior pre-catalyst in regioselective hydroboration of quinolines has also been demonstrated.

Authors with CRIS profile

Daniel Maximilian Pividori Lehrstuhl für Anorganische und Allgemeine Chemie Dominik Fehn Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Technische Universität Berlin DE Germany (DE) Xiamen University CN China (CN)

How to cite

APA:

Kalra, S., Pividori, D.M., Fehn, D., Dai, C., Dong, S., Yao, S.,... Driess, M. (2022). A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d(7)-Mn(CO)(5) radical. Chemical Science. https://dx.doi.org/10.1039/d2sc03352f

MLA:

Kalra, Shweta, et al. "A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d(7)-Mn(CO)(5) radical." Chemical Science (2022).

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