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Merck

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
Argon, ≥99.998%
Sigma-Aldrich
Tetrahydrofuran, anhydrous, ≥99.9%, inhibitor-free
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1,4-Dimethoxybenzene, ReagentPlus®, 99%
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Rhein, technical grade
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Acetonitrile solution, contains 0.1 % (v/v) trifluoroacetic acid, suitable for HPLC
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Lithium aluminum hydride, pellets, reagent grade, 95%
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Lithium aluminum hydride, powder, reagent grade, 95%
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1,4-Dimethoxybenzene, 99%, FG
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Tetrahydrofuran, anhydrous, contains 250 ppm BHT as inhibitor, ≥99.9%
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Tetrahydrofuran, suitable for HPLC, ≥99.9%, inhibitor-free
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Rhein
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Sodium tert-pentoxide solution, 1.4 M in THF
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Lithium aluminum hydride, ≥97.0% (gas-volumetric)
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Tetrahydrofuran, suitable for HPLC, contains no stabilizer
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Lithium aluminum hydride, hydrogen-storage grade
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Acetonitrile solution, contains 0.05 % (w/v) ammonium formate, 5 % (v/v) water, 0.1 % (v/v) formic acid, suitable for HPLC
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