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A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d7-Mn(CO)5 radical.

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, {κ3-[SiNSi]Mn(dmpe)} 4 (dmpe = (Me2P)2C2H4), 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 π-acceptor ligands CO and 2,6-dimethylphenyl isocyanide afforded the related Mn(0) complexes κ2-[SiNSi]Mn(CO)3 (5) and κ3-[SiNSi]Mn(CNXylyl)2(κ1-dmpe) (6), respectively. Remarkably, the stabilization of Mn(0) in the coordination sphere of the [SiNSi] ligand favors the d7 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.

SUBMITTER: Kalra S 

PROVIDER: S-EPMC9337724 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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

Kalra Shweta S   Pividori Daniel D   Fehn Dominik D   Dai Chenshu C   Dong Shicheng S   Yao Shenglai S   Zhu Jun J   Meyer Karsten K   Driess Matthias M  

Chemical science 20220706 29

Using the potentially tridentate <i>N</i>,<i>N'</i>-bis(<i>N</i>-heterocyclic silylene)pyridine [SiNSi] pincer-type ligand, 2,6-<i>N</i>,<i>N'</i>-diethyl-bis[<i>N</i>,<i>N'</i>-di-<i>tert</i>-butyl(phenylamidinato)silylene] diaminopyridine, led to the first isolable bis(silylene)pyridine-stabilized manganese(0) complex, {κ<sup>3</sup>-[SiNSi]Mn(dmpe)} 4 (dmpe = (Me<sub>2</sub>P)<sub>2</sub>C<sub>2</sub>H<sub>4</sub>), which represents an isolobal 17 VE analogue of the elusive Mn(CO)<sub>5</sub>  ...[more]

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