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Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides.

Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides.

Chemistry (Weinheim an der Bergstrasse, Germany) (2015-06-11)

Brandon K Tate, Jenna T Nguyen, John Bacsa, Joseph P Sadighi

ABSTRACT

Alkoxide-bridged disilver cations react with dihydrogen to form hydride-bridged cations, releasing free alcohol. Hydrogenolysis of neutral silver fluorides affords hydride-bridged disilver cations as their bifluoride salts. These reactions proceed most efficiently when the supporting ligands are expanded N-heterocyclic carbenes (NHCs) derived from 6- and 7-membered cyclic amidinium salts. Kinetics studies show that silver fluoride hydrogenolysis is first-order in both silver and dihydrogen.

MATERIALS

Product Number

Brand

Product Description

Sigma-Aldrich

Deuterium oxide, 99.9 atom % D, contains 1 % (w/w) 3-(trimethylsilyl)-1-propanesulfonic acid, sodium salt (DSS)

Sigma-Aldrich

Pentane, anhydrous, ≥99%

Sigma-Aldrich

Calcium hydride, purum p.a., ≥97.0% (gas-volumetric), powder

Sigma-Aldrich

Calcium hydride, powder, 0-2 mm, reagent grade, ≥90% (gas-volumetric)

Sigma-Aldrich

Acetonitrile, ≥99.5%, ACS reagent

Sigma-Aldrich

Dichloromethane, anhydrous, ≥99.8%, contains 40-150 ppm amylene as stabilizer

Sigma-Aldrich

Acetonitrile, anhydrous, 99.8%

Sigma-Aldrich

Deuterium oxide, 99.9 atom % D, contains 0.75 wt. % 3-(trimethylsilyl)propionic-2,2,3,3-d₄ acid, sodium salt

Sigma-Aldrich

Dichloromethane, suitable for HPLC, ≥99.9%, contains 40-150 ppm amylene as stabilizer

Sigma-Aldrich

Calcium hydride, powder, 99.99% trace metals basis

Sigma-Aldrich

Toluene, anhydrous, 99.8%

Sigma-Aldrich

Deuterium oxide, 99.9 atom % D

Sigma-Aldrich

Sodium tert-pentoxide, 95%

Sigma-Aldrich

Deuterium, 99.8 atom % D

Sigma-Aldrich

Acetonitrile, ≥99.8%, suitable for HPLC

Sigma-Aldrich

Toluene, JIS 300, for residue analysis, ≥99.8%

Sigma-Aldrich

Dichloromethane, JIS special grade, ≥99.0%

Sigma-Aldrich

Toluene, SAJ first grade, ≥99.0%

Sigma-Aldrich

Acetonitrile, for chromatography

Sigma-Aldrich

Acetonitrile, for residue analysis, JIS 5000

Sigma-Aldrich

Dichloromethane, JIS 300, for residue analysis

Sigma-Aldrich

Deuterium oxide, 99.9 atom % D, contains 0.05 wt. % 3-(trimethylsilyl)propionic-2,2,3,3-d₄ acid, sodium salt

Sigma-Aldrich

Benzene, anhydrous, 99.8%

Sigma-Aldrich

Pentane, SAJ special grade, ≥99.0%

Sigma-Aldrich

Acetonitrile, ≥99.8%, for residue analysis, JIS 300

Sigma-Aldrich

Pentane, SAJ first grade, ≥96.0%

Sigma-Aldrich

Toluene, JIS 1000, for residue analysis, ≥99.8%

Sigma-Aldrich

Dichloromethane, SAJ first grade, ≥99.0%

Sigma-Aldrich

Benzene, JIS 300, ≥99.5%, for residue analysis

Sigma-Aldrich

Acetonitrile, ≥99.8%, for residue analysis, JIS 1000