Missing Reactivity of Trimethylsilyl Reagents: Dehalogenative Activation Enabling One-Pot Generation of Aryne from 2-Iodophenol

10.26434/chemrxiv.7934987 ◽

2019 ◽

Author(s):

Koichiro Mikami ◽

Takaaki Hirano ◽

Hanamura Hitoshi

Keyword(s):

Exchange Reaction ◽

Halogen Atom ◽

Metal Exchange ◽

One Pot ◽

Metal Exchange Reaction ◽

The One

Herein we present a missing reactivity of trimethylsilyl reagents; dehalogenative activation, which involves abstracting a halogen atom and anionically activating the substrate similar to the halogen-metal exchange reaction in classical carbanion species. This missing reactivity allowed for the one-pot generation of aryne from 2-iodophenol.

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Magnesium(II) and cadmium(II) octaphenyltetraazaporphyrinates in metal exchange reaction with MnCl2 in DMSO

Russian Journal of Inorganic Chemistry ◽

10.1134/s0036023617040222 ◽

2017 ◽

Vol 62 (4) ◽

pp. 517-522 ◽

Cited By ~ 1

Author(s):

S. V. Zvezdina ◽

N. V. Chizhova ◽

N. Zh. Mamardashvili

Keyword(s):

Exchange Reaction ◽

Metal Exchange ◽

Metal Exchange Reaction

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The Second Step of the Halogen/Metal Exchange Reaction

Organic Letters ◽

10.1021/ol027307i ◽

2003 ◽

Vol 5 (3) ◽

pp. 313-316 ◽

Cited By ~ 14

Author(s):

Reinhard W. Hoffmann ◽

Mark Brönstrup ◽

Michael Müller

Keyword(s):

Exchange Reaction ◽

Second Step ◽

Metal Exchange ◽

Metal Exchange Reaction

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Thermochromism of Metal Exchange Reaction between Zinc(II) and Mercury(II) Porphyrins

Zeitschrift für Naturforschung B ◽

10.1515/znb-1995-0412 ◽

1995 ◽

Vol 50 (4) ◽

pp. 545-550 ◽

Cited By ~ 1

Author(s):

Masaaki Tabata ◽

Masahiro Ide ◽

Kentaro Kaneko

Keyword(s):

Aqueous Solution ◽

Exchange Reaction ◽

Thermodynamic Parameters ◽

Distribution Curve ◽

Equilibrium Constants ◽

Metal Exchange ◽

Free Base ◽

Temperature Range ◽

Base Form ◽

Metal Exchange Reaction

Thermochromism was observed for an aqueous solution containing zinc(II) and mercury( II) cations and N-p-nitrobenzyl-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (NO2Bz(Htpps)4-) in the temperature range 10 to 70 °C. The equilibrium constants and the thermodynamic parameters of Zn(NO2Bztpps)3- and Hg(NO2Bztpps)3- have been determined spectrophotometrically to elucidate the thermochromism at 10, 15, 20, 25 and 30 °C in 0.1 mol dm-3 NaNO3. The protonation and metalation constants of NO2Bz(Htpps)4- are defined as K2 = [H2P][H+]-1[HP]-1, K3 = [H3P][H+]-1[H2P]-1 and KMP = [M P][H+][M2+]-1[HP]-1, where HP and MP denote the free base form of the prophyrin and the metalloporphyrins of zinc(II) and mercury(II), respectively. Charges of the prophyrin and metalloporphyrins are omitted for simplicity. The following values were found: logK2 = 7.75 ±0.02 (25 °C), ΔH°/kJmol-1 = -21.2±0.5 and ΔS°/Jmol-1K-1 = 77±1, logK3 = 2.55±0.02 (25 °C), ΔH°/kJmol-1 = -25±0.8 and ΔS°/Jmol-1K-1 = -35±3 and log KZnP = 0.63±0.03 (25 °C), ΔH°/kJmol-1 = 31.0±0.8 and ΔS°/Jmol-1K-1 = 116±3, logKHgP = 6.22±0.03 (25 °C), ΔH°/kJmol-1 = 4.5±0.7 and ΔS°/Jmol-1K-1 = 134±2. The distribution curve calculated from the thermodynamic parameters sufficiently agrees with the observed metal exchange reaction between the metalloporphyrins.

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