Bildungsmechanismus und eigenschaften von Phenyläthinyl-triphenylphosphoniumbromid

Hoffmann, H.; Förster, Heinz

doi:10.1016/s0040-4039(00)90417-9

Cited by 25 publications

(9 citation statements)

References 3 publications

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“…CD 3 CN accelerates the reaction, leading to a yield of 60% in 50 min. In the presence of water (0.6 equiv) in CD 3 CN, the same yield was observed, along with the decomposition of 5a to Ph 3 PO and the terminal alkyne, as well as 1,4-bisphenylbuta-1,3-diyne being formed by the coupling of the terminal alkyne with the alkynylgold(III) complex (see SI section 4.3). We have also confirmed that the oxidative addition behavior is not specific to Phen complex 1a , and the complex (2,2′-bipyridyl)Ph 3 PAu(I)NTf 2 1e is also competent for the oxidative addition, giving the product in 38% NMR yield after 12 h.…”

Section: Resultsmentioning

confidence: 60%

Trans Influence of Ligands on the Oxidation of Gold(I) Complexes

et al. 2019

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Gold(I) complexes are considered active species toward oxidative addition; current understanding indicates a different mechanism in contrast to other late transition metals, but a rational understanding of the reactivity profile is lacking. Herein, we propose that the accessibility of the gold(I) center to tri-or tetracoordination is critical in the oxidative process involving a tri-or tetra-coordinate gold(I) with the oxidizing reagent as one of the ligands as an intermediate. A computational study of the geometry of (Phen)R 3 PAu(I)NTf 2 complexes shows that the accessibility of such tricoordinate species shows a good correlation with the "trans influence" of phosphine ligands: the weak σ-donating phosphine ligands promote tricoordination of gold(I) complexes. The oxidative addition to the asymmetric tricoordinate (Phen)R 3 PAu(I)NTf 2 complexes with alkynyl hypervalent iodine reagents was built. The kinetic profile of the oxidative addition exhibits a good relationship to the Hammett substituent parameter (ρ = 3.75, R 2 = 0.934), in which the gold(I) complexes bearing less σ-donating phosphine ligands increase the rate of oxidative addition. The positive ρ indicates a high sensitivity of the oxidative addition to the trans influence. The reactivity profile of oxidative addition to a linear bis(pyridine)gold(I) complex further supports that the oxidative addition to gold(I) complexes is promoted by ligands with small trans influence.

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Section: Resultsmentioning

confidence: 60%

Trans Influence of Ligands on the Oxidation of Gold(I) Complexes

et al. 2019

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“…The IR spectra of these salts exhibit absorption bands of moderate intensity at about 2150 ± 2200 cm 71 . In aqueous solutions, anion exchange is possible, for example, bromide can be replaced by iodide, 253 and chloride can be replaced by chloroplatinate. 249 On heating with water or acetic acid, the acetylene fragment in the salts 519 is hydrated giving a carbonyl group at the carbon atom furthest from phosphorus.…”

Section: Alkynylphosphonium Cationsmentioning

confidence: 99%

“…249 On heating with water or acetic acid, the acetylene fragment in the salts 519 is hydrated giving a carbonyl group at the carbon atom furthest from phosphorus. 252,253 Recently, preparation of alkynylphosphonium salts 521 by treatment of alkynyliodonium salts 520 with polycyclic trialkylphosphines has been described 524 (see Section VII.3).…”

Section: Alkynylphosphonium Cationsmentioning

confidence: 99%

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Alkynylcarbenium ions and related unsaturated cations

Lukyanov¹,

Koblik²,

Muradyan³

1998

Russ. Chem. Rev.

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“…(15) bilden. In Alkohol solvolysiert das p r i m a r e Ionenpaar (14) zu Trihalogenmethan, Phosphinoxyd und Alkylhalogenid [ 181 : N. B. Desui, B. Hansen u. N Der Umsetzung der a-Halogen-carbonyl-Verbindungen mit Phosphinen zu den Keto-und Enolphosphoniumsalzen entsprechen zwei ahnliche Reaktionen rnit tertiaren Phosphiten: Die Ketophosphonester-Bildung -…”

Section: Chohunclassified

Die Phosphoniumsalz‐Bildung zweiter Art

Hoffmann

Diehr

1964

Angewandte Chemie

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man 0,05 Mol der Monocarbonylverbindung zu und IiRt die Reaktion unter intensivem Riihren ablaufen. Zur Neutralisation wird eine Losung von 0,l Mol NH4CI in 200 ml Wasser zugefiigt. 9-Phenylathinyl-xanthydrol (39b)Bei einer Reaktionszeit von 24 Std. wurde die Verbindung (3Yb) nach Methode E aus atherischer Losung in 83-proz.Ausbeute erhalten, Fp = 122 "C. Methode F [l5]Die Carbonylverbindung wird in inertem Losungsmittel (Toluol) in Gegenwart von gepulvertem KOH zur Reaktion gebracht.

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Bildungsmechanismus und eigenschaften von Phenyläthinyl-triphenylphosphoniumbromid

Cited by 25 publications

References 3 publications

Trans Influence of Ligands on the Oxidation of Gold(I) Complexes

Trans Influence of Ligands on the Oxidation of Gold(I) Complexes

Alkynylcarbenium ions and related unsaturated cations

Die Phosphoniumsalz‐Bildung zweiter Art

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