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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, 99.8 atom % D
Sigma-Aldrich
Dichloromethane, suitable for HPLC, ≥99.9%, contains 40-150 ppm amylene as stabilizer
Sigma-Aldrich
Toluene, anhydrous, 99.8%
Sigma-Aldrich
Calcium hydride, powder, 0-2 mm, reagent grade, ≥90% (gas-volumetric)
Sigma-Aldrich
Acetonitrile, anhydrous, 99.8%
Sigma-Aldrich
Pentane, anhydrous, ≥99%
Sigma-Aldrich
Sodium tert-pentoxide, 95%
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
Deuterium hydride, extent of labeling: 96 mol% DH, 98 atom % D
Sigma-Aldrich
Benzene, anhydrous, 99.8%
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
Calcium hydride, reagent grade, 95% (gas-volumetric)
Sigma-Aldrich
Dichloromethane, anhydrous, ≥99.8%, contains 40-150 ppm amylene as stabilizer
Sigma-Aldrich
Deuterium, 99.96 atom % D
Sigma-Aldrich
Deuterium oxide, filtered, 99.8 atom % D
Sigma-Aldrich
Calcium hydride, 99.9% trace metals basis
Sigma-Aldrich
Deuterium, 99.9 atom % D
Sigma-Aldrich
Deuterium oxide, 99.9 atom % D, contains 1 % (w/w) 3-(trimethylsilyl)-1-propanesulfonic acid, sodium salt (DSS)
Sigma-Aldrich
Calcium hydride, purum p.a., ≥97.0% (gas-volumetric), powder
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Argon-40Ar, 99.95 atom %
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Deuterium oxide, 60 atom % D
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Deuterium oxide, 70 atom % D
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Acetonitrile, electronic grade, 99.999% trace metals basis
Sigma-Aldrich
Deuterium oxide, 99.9 atom % D
Sigma-Aldrich
Calcium hydride, powder, 99.99% trace metals basis
Sigma-Aldrich
Ultrapure Acetonitrile
Sigma-Aldrich
Sodium tert-pentoxide solution, 1.4 M in THF
Sigma-Aldrich
Lithium aluminum hydride, hydrogen-storage grade
Sigma-Aldrich
Lithium aluminum hydride, ≥97.0% (gas-volumetric)
Sigma-Aldrich
Lithium aluminum hydride, pellets, reagent grade, 95%