New cationic coinage metal complexes featuring silyl group functionalized phosphine: syntheses, structures and catalytic studies in alkyne-azide cycloaddition reactions.
Dalton Trans
; 52(42): 15549-15561, 2023 Oct 31.
Article
em En
| MEDLINE
| ID: mdl-37753593
ABSTRACT
A series of coinage metal complexes bearing rarely explored ortho-silylated phosphine is reported. The treatment of diphenyl(2-(trimethylsilyl)phenyl)phosphine (1) with CuCl and [Cu(CH3CN)4]BF4 furnished the corresponding neutral [(1)CuCl]2 (2) and mono-cationic [(1)2Cu(CH3CN)]BF4 (3) complexes, respectively. The reactions of 1 with AgX (X = BF4-, NO3-) in 2 1 ratio furnished the corresponding mono cationic dicoordinate silver(I) complexes of the type [(1)2Ag]X (X = BF4- (4a), NO3- (4b)). The ortho-silylated phosphine ligand (1) was conveniently converted into the corresponding sulfide (5a) and selenide (5b) species, and their reactions with [Cu(CH3CN)4]BF4 yielded mono-cationic, homoleptic tris(silylphosphinochalcogenide)copper(I) complexes of the type [(5a/5b)3Cu]BF4 (6a/6b). The molecular structures of 2-4 and 6 were established by single-crystal X-ray diffraction analysis. The copper complexes 2, 3, and 6a were employed as catalysts in azide-alkyne cycloaddition reactions. Among these complexes, 3 was extensively used in the preparation of various mono- and bis-triazoles consisting of tolyl, benzyl, carbazolyl, and propargylic ether groups. Three sets of substituted triazole derivatives were achieved under mild conditions by employing copper(I) catalytic systems. The mechanistic studies indicated the formation of a heteroleptic copper(I) triazolide intermediate which was detected by high-resolution mass spectral analysis.
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MEDLINE
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Ano de publicação:
2023
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Article