Hydrodechlorination of Et3NBCl3 Catalyzed by Amorphous Nickel Boride – A Mechanistic Approach. Issue 3 (9th December 2013)

• Record Type: Journal Article
• Authors: Reller, Christian; Mertens, Florian O. R. L.
• Is Part Of: European journal of inorganic chemistry. Issue 3(2014)
• Page Start: 450
• Page End: 459
• Publication Date: 2013-12-09
• Subjects: Heterogeneous catalysis -- Hydrodehalogenation -- Boranes -- Nickel boride -- Deuterium labeling -- Reaction mechanisms; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301253
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The catalytic hydrodechlorination of BCl3 with molecular hydrogen in the presence of tertiary amines is a viable strategy for the energy‐efficient generation of valuable B–H bonds. A mechanistic study based on experiments with isolated intermediates and deuterium labeling experiments is presented. The occurrence of the rate‐limiting reverse reaction from the insoluble Et3 NHCl adduct was identified as a major cause of low Et3 NBH3 yields. In addition, amines with NCH2 units, which also serve in the corresponding cases as solvents, have a strong influence on the reaction kinetics; they are directly involved in the hydrogen transfer at elevated temperatures and assume the role of a cocatalyst. A catalytic cycle for the reaction on a nickel boride catalyst is proposed. Abstract : The mechanistic aspects of the generation of borane species from BCl3 by catalytic hydrodechlorination with molecular hydrogen in the presence of tertiary amines are investigated. The NCH2 units of the amines are particularly important to the overall reaction kinetics and these units are assigned the role of cocatalyst. Equilibrium investigations guide the way for the improvement of the synthesis.