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• W2023803577 abstract "(Me3P)Au(C⋮CPh)3 (1) was prepared as the first trialkynylgold(III) complex via three different routes: Treatment of solvated AuCl3 with 3 equiv of PhC⋮CLi in the presence of PMe3, or of (Me3P)AuBr2Cl with the same reagent, gives high to medium yields of the product (1), which is also available from equimolar quantities of (Me3P)AuC⋮CPh and (PhC⋮C)2TlCl. The same reactions fail with less powerful donors (PPh3) or more bulky ligands (PiPr3). The products of reductive elimination, PhC⋮CC⋮CPh and (R3P)AuC⋮CPh, are obtained instead. The molecular structure of compound 1 has been determined from single crystals of a monoclinic, solvent-free phase and a triclinic 1:1 solvate (1)·CH2Cl2. In the square-planar environment of the gold(III) center one of the three phenylethynyl groups exhibits the trans influence of the PMe3 ligand. The reactions of 1 with PPh3, HCl, and I2 were studied, but no stable functional poly(alkynyl)gold(III) compounds could be isolated. Serendipitously, single crystals of a byproduct, [(PhC⋮C)Me2PCH2Au(C⋮CPh)3], were found to grow from one of the reaction mixtures. The molecular structure has been determined, but no efficient synthetic pathway could be found. Salts with the tetra(phenylethynyl)aurate(III) anion [Au(C⋮CPh)4]- were obtained from compound 1 upon treatment with PhC⋮CLi. The complex ion undergoes facile reductive elimination of PhC⋮CC⋮CPh to produce the [Au(C⋮CPh)2]- anion. After metathesis with nBu4N+Br-, mixed-anion salts with nonstoichiometric composition were precipitated as colorless, diamagnetic solids. From this product mixture, single crystals with the anion ratio 1:1 could be grown for structure determination: [nBu4N]2[Au(C⋮CPh)4][Au(C⋮CPh)2]·(CH2Cl2). The structure of the reference compound [nBu4N][Au(C⋮CPh)2] has also been determined. The anions have square-planar and linear structures, respectively, with very small variations in the bond distances and angles." @default.
• W2023803577 created "2016-06-24" @default.
• W2023803577 creator A5036764619 @default.
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• W2023803577 date "2005-03-31" @default.
• W2023803577 modified "2023-10-11" @default.
• W2023803577 title "Preparative Routes to the First Tri- and Tetra(alkynyl)gold(III) Compounds: (L)Au(C⋮CR)₃ and [ER₄]⁺ [Au(C⋮CR)₄]^-" @default.
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• W2023803577 doi "https://doi.org/10.1021/om050038q" @default.
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