Stepwise azido transfer to cerous tris(tert-butoxy)siloxide via trans-silylation with Me3SiN3†

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-07-21 DOI:10.1039/D5DT01051A

Jochen Friedrich, Jonas Riedmaier, Cäcilia Maichle-Mössmer and Reiner Anwander

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Abstract

Trimethylsilylhalogenides and -pseudohalogenides are frequently used reactants for (pseudo)halogen transfer, including derivatizations of cerium compounds. The present study describes the facile ligand exchange of cerium(III) complex [Ce{OSi(OtBu)₃}₃]₂ with Me₃SiN₃ generating the mixed azido/siloxy Ce^III complexes Ce₂[OSi(OtBu)₃]₅(N₃) and [Ce{OSi(OtBu)₃}₂(N₃)]₄. Although cerium siloxide complexes are a topical research field, thermal or photolytic ligand degradation as described in Ce^IV alkoxide chemistry has not been described. The activation of the azide complexes by irradiation with UV-visible light is easily achieved for such mixed azido/siloxy cerous complexes, as revealed by the identification of the homoleptic ceric complex Ce[OSi(OtBu)₃]₄.

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通过与Me3SiN3的转硅化，叠氮基逐步转移到铈三（叔丁基）氧化硅

三甲基硅基卤化物和-伪卤化物是（伪）卤素转移常用的反应物，包括铈化合物的衍生化。本研究描述了铈（III）配合物[Ce{OSi(OtBu)3]3]2与Me3SiN3的易配体交换，生成了混合叠氮/硅氧基CeIII配合物Ce2[OSi(OtBu)3]5（N3）和[Ce{OSi(OtBu)3}2(N3)]4。虽然硅氧化铈配合物是一个热门的研究领域，但在CeIV醇氧化合物化学中描述的热或光解配体降解尚未被描述。叠氮化物配合物的热活化和紫外可见照射对于这种混合叠氮化物/硅氧铈配合物是很容易实现的，提供了同感铈配合物Ce[OSi(OtBu)3]4作为可分离的化合物。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.