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Title: Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-Defined Manganese(II) Complex
Authors: Brzozowska, Aleksandra
Azofra Mesa, Luis Miguel 
Zubar, Viktoriia
Atodiresei, Iuliana
Cavallo, Luigi
Rueping, Magnus
El-Sepelgy, Osama
UNESCO Clasification: 221001 Catálisis
Issue Date: 2018
Journal: ACS Catalysis 
Abstract: Herein we report unprecedented manganese-catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor. The reaction is catalyzed by a pincer complex of the earth-abundant manganese(II) salt in the absence of any additives, base, or superhydride. The ammonia borane smoothly reduces the manganese precatalyst [Mn(II)–PNP][Cl]2 to the catalytically active species [Mn(I)–PNP]–hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational density functional theory (DFT) analysis studies of the reaction mechanism rationalize the origin of stereoselectivity toward formation of (Z)-alkenes.
ISSN: 2155-5435
DOI: 10.1021/acscatal.8b00983
Source: ACS Catalysis [ISSN 2155-5435], v. 8, 5, p. 4103-4109
Appears in Collections:Artículos
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