Two Faces of the Bi-O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si-O Bond Formation

被引：15
|
作者：
Ramler, Jacqueline [1 ]
Schwarzmann, Johannes [1 ]
Stoy, Andreas [1 ,2 ]
Lichtenberg, Crispin [1 ,2 ]
机构：
[1] Julius Maximilians Univ Wurzbur, Inst Inorgan Chem, D-97074 Wurzburg, Germany
[2] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35032 Marburg, Germany
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2022年 / 2022卷 / 07期
基金：
欧洲研究理事会;
关键词：
Bismuth; Catalysis; Chalcogens; Dehydrocoupling; Radical reactions; LIVING RADICAL POLYMERIZATION; ORGANOBISMUTH COMPOUNDS; BISMUTH(III) COMPOUNDS; OXIDATIVE ADDITION; CARBON-DIOXIDE; HYDROGEN; CRYSTAL; LIGAND; ACTIVATION; REACTIVITY;
D O I：
10.1002/ejic.202100934
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The diorgano(bismuth)alcoholate [Bi((C6H4CH2)(2)S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi-O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed-shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations.
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页数：6
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