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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

Lithium aluminum hydride, pellets, reagent grade, 95%

Sigma-Aldrich

Lithium aluminum hydride, ≥97.0% (gas-volumetric)

Sigma-Aldrich

Lithium aluminum hydride, powder, reagent grade, 95%

Sigma-Aldrich

Lithium aluminum hydride, ≥97.0% (gas-volumetric), tablet (5 g each)

Sigma-Aldrich

Lithium aluminum hydride, hydrogen-storage grade

Sigma-Aldrich

Tetrahydrofuran, anhydrous, contains 250 ppm BHT as inhibitor, ≥99.9%

Sigma-Aldrich

Rhein, technical grade

Sigma-Aldrich

Tetrahydrofuran, contains 250 ppm BHT as inhibitor, ACS reagent, ≥99.0%

Sigma-Aldrich

Tetrahydrofuran, suitable for HPLC, ≥99.9%, inhibitor-free

Sigma-Aldrich

1,4-Dimethoxybenzene, 99%, FG

Sigma-Aldrich

Argon, ≥99.998%

Sigma-Aldrich

Toluene, anhydrous, 99.8%

Sigma-Aldrich

1,4-Dimethoxybenzene, ReagentPlus^®, 99%

Sigma-Aldrich

Rhein

Sigma-Aldrich

Acetonitrile solution, contains 0.1 % (v/v) trifluoroacetic acid, suitable for HPLC

Sigma-Aldrich

Sodium tert-pentoxide solution, 1.4 M in THF

Sigma-Aldrich

Sodium tert-pentoxide solution, 40% in toluene

Sigma-Aldrich

Tetrahydrofuran, anhydrous, ≥99.9%, inhibitor-free

Sigma-Aldrich

Benzene, anhydrous, 99.8%

Sigma-Aldrich

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

Sigma-Aldrich

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

Sigma-Aldrich

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

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

Deuterium hydride, extent of labeling: 96 mol% DH, 98 atom % D

Sigma-Aldrich

Deuterium oxide, 99 atom % D

Sigma-Aldrich

Calcium hydride, powder, 99.99% trace metals basis