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

Sigma-Aldrich

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

Sigma-Aldrich

Lithium aluminum hydride, pellets, reagent grade, 95%

Sigma-Aldrich

Lithium aluminum hydride, powder, reagent grade, 95%

Sigma-Aldrich

Lithium aluminum hydride, hydrogen-storage grade

Sigma-Aldrich

Sodium tert-pentoxide solution, 40% in toluene

Sigma-Aldrich

Sodium tert-pentoxide solution, 1.4 M in THF

Sigma-Aldrich

Rhein

Sigma-Aldrich

1,4-Dimethoxybenzene, 99%, FG

Sigma-Aldrich

Rhein, technical grade

Sigma-Aldrich

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

Sigma-Aldrich

Toluene, anhydrous, 99.8%

Sigma-Aldrich

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

Sigma-Aldrich

Benzene, anhydrous, 99.8%

Sigma-Aldrich

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

Supelco

Dichloromethane, ≥99.9%

Sigma-Aldrich

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

Sigma-Aldrich

Deuterium oxide, filtered, 99.8 atom % D

Sigma-Aldrich

Argon-⁴⁰Ar, 99.95 atom %

Sigma-Aldrich

Deuterium oxide, 70 atom % D

Sigma-Aldrich

Deuterium oxide, 60 atom % D

Sigma-Aldrich

Ultrapure Acetonitrile

Sigma-Aldrich

Acetonitrile, electronic grade, 99.999% trace metals basis

Sigma-Aldrich

Sodium tert-pentoxide, 95%

Sigma-Aldrich

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

Sigma-Aldrich

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