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双（硅烯）吡啶钳形配体可稳定单核锰（0）配合物：便捷合成难以捉摸的d-Mn(CO)自由基的可分离类似物。

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

作者信息

Kalra Shweta, Pividori Daniel, Fehn Dominik, Dai Chenshu, Dong Shicheng, Yao Shenglai, Zhu Jun, Meyer Karsten, Driess Matthias

机构信息

Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin Strasse des 17. Juni 135, Sekr. C2 D-10623 Berlin Germany

Inorganic Chemistry, Department of Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) Egerlandstrasse 1 91058 Erlangen Germany.

出版信息

Chem Sci. 2022 Jul 6;13(29):8634-8641. doi: 10.1039/d2sc03352f. eCollection 2022 Jul 29.

DOI:10.1039/d2sc03352f
PMID:35974753
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9337724/
Abstract

Using the potentially tridentate ,-bis(-heterocyclic silylene)pyridine [SiNSi] pincer-type ligand, 2,6-,-diethyl-bis[,-di--butyl(phenylamidinato)silylene] diaminopyridine, led to the first isolable bis(silylene)pyridine-stabilized manganese(0) complex, {κ-[SiNSi]Mn(dmpe)} 4 (dmpe = (MeP)CH), which represents an isolobal 17 VE analogue of the elusive Mn(CO) 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 κ-[SiNSi]Mn(CO) (5) and κ-[SiNSi]Mn(CNXylyl)(κ-dmpe) (6), respectively. Remarkably, the stabilization of Mn(0) in the coordination sphere of the [SiNSi] ligand favors the d 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.

摘要

使用具有潜在三齿的、-双（-杂环硅烯）吡啶[SiNSi]钳型配体，2,6-，-二乙基-双[，-二-丁基（苯脒基）硅烯]二氨基吡啶，得到了首个可分离的双（硅烯）吡啶稳定化的锰（0）配合物{κ-[SiNSi]Mn(dmpe)} 4（dmpe = (MeP)CH），它代表了难以捉摸的Mn(CO)自由基的等瓣17价电子类似物。该化合物可通过用石墨钾对相应的二卤代（SiNSi）Mn(ii)配合物1（Cl）和2（Br）进行还原脱卤来制备。将4暴露于更强的π-受体配体CO和2,6-二甲基苯基异氰化物中，分别得到了相关的Mn(0)配合物κ-[SiNSi]Mn(CO)（5）和κ-[SiNSi]Mn(CNXylyl)(κ-dmpe)（6）。值得注意的是，如电子顺磁共振光谱、超导量子干涉仪测量和密度泛函理论计算所示，在[SiNSi]配体的配位球中Mn(0)的稳定化有利于d低自旋电子构型。4作为喹啉区域选择性硼氢化反应中优良预催化剂的适用性也得到了证明。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/dec69dca69b6/d2sc03352f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/7cad900e4f7d/d2sc03352f-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/87bef6507509/d2sc03352f-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/9e9979cb6c39/d2sc03352f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/06a0e9ad059d/d2sc03352f-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/dec69dca69b6/d2sc03352f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/7cad900e4f7d/d2sc03352f-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/5510ee531fae/d2sc03352f-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/4496234c3bd4/d2sc03352f-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/87bef6507509/d2sc03352f-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/9e9979cb6c39/d2sc03352f-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/04fb/9337724/dec69dca69b6/d2sc03352f-s2.jpg

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