2022
DOI: 10.1002/chem.202203181
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Terminal Au−N and Au−O Units in Organometallic Frames

Abstract: Since gold is located well beyond the oxo wall, chemical species with terminal AuÀ N and AuÀ O units are extremely rare and limited to low coordination numbers. We report here that these unusual units can be trapped within a suitable organometallic frame. Thus, the terminal auronitrene and auroxyl derivatives [(CF 3 ) 3 AuN] À and [(CF 3 ) 3 AuO] À were identified as local minima by calculation. These open-shell, high-energy ions were experimentally detected by tandem mass spectrometry (MS 2 ): They respective… Show more

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Cited by 9 publications
(9 citation statements)
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“…The alkyl group functions as an electron-donating moiety, augmenting the electronegativity of the nitrogen atom to generate RNH 3 + . When OA comes into contact with Au(III), the coordination of RNH 3 + with Au(III) results in the formation of Au(III)-OA through a phase transfer [ 22 , 36 ]. When the equilibrium is reached in the diffusion of Au(III) between two phases, the concentration ratio of Au(III) in the oil phase to that in the aqueous phase is referred to as the diffusion equilibrium constant (K 1 = 6.95).…”
Section: Resultsmentioning
confidence: 99%
“…The alkyl group functions as an electron-donating moiety, augmenting the electronegativity of the nitrogen atom to generate RNH 3 + . When OA comes into contact with Au(III), the coordination of RNH 3 + with Au(III) results in the formation of Au(III)-OA through a phase transfer [ 22 , 36 ]. When the equilibrium is reached in the diffusion of Au(III) between two phases, the concentration ratio of Au(III) in the oil phase to that in the aqueous phase is referred to as the diffusion equilibrium constant (K 1 = 6.95).…”
Section: Resultsmentioning
confidence: 99%
“…The Au–ONO 2 distance (2.133(2) Å) is similar to that found in [Au(CH 2 COMe)(ONO 2 )(ppy)] (2.128(3) Å; ppy = 2-phenylen-2′-yl-pyridine) 75 but longer than in [Au(CF 3 ) 3 (ONO 2 )] (2.090(4) Å). 76 In both 5a ·H 2 O and 6a , the trifluoromethyl and phosphine ligands are in a mutual trans disposition.…”
Section: Resultsmentioning
confidence: 99%
“…The Au−ONO 2 distance (2.133(2) Å) is similar to that found in [ (CH 2 COMe)(ONO 2 )(ppy)] (2.128(3) Å; ppy = 2-phenylen-2′-yl-pyridine) 75 but longer than in [Au(CF 3 ) 3 (ONO 2 )] (2.090(4) Å). 76 In both 5a•H 2 O and 6a, the trifluoromethyl and phosphine ligands are in a mutual trans disposition. The 19 F and 31 P{ 1 H} NMR spectra of 3a−9a, 11a, 3b, 4b, and 8b showed a doublet and a quartet, respectively, with a large 3 J PF value (62.4−72.8 Hz) characteristic of a mutually trans arrangement of the phosphine and trifluoromethyl ligands.…”
Section: ■ Introductionmentioning
confidence: 99%
“…The ILF theory, nowadays well supported by experimental data and calculations, [1,5–16] provides a critical review of the high formal oxidation state in 11 th group metals suggesting that most of the d 8 Cu(III) and Au(III) square planar complexes could be better considered as d 10 Cu(I) and Au(I) ones with electronic holes on the ligands. This new bond description allows a better knowledge of the reactivity of these systems, not always easily to be rationalized.…”
Section: Introductionmentioning
confidence: 97%