Cationic PCP and PCN NHC Core Pincer-Type Mn(I) Complexes: From Synthesis to Catalysis - Archive ouverte HAL
Journal Articles Organometallics Year : 2021

Cationic PCP and PCN NHC Core Pincer-Type Mn(I) Complexes: From Synthesis to Catalysis

Abstract

The coordination chemistry of NHC core pincer-type PCP and PCN ligands with Mn(I) center was systematically investigated. The reaction of [Mn(CO)5Br] with free carbenes, conveniently prepared from the corresponding imidazolium salts and a strong base, lead to the initial formation of bidentate fac-[MnBr(CO)3(κ 2 P,C,L)] complexes bearing a pending phosphine or pyridine donor extremity (L), which upon bromide abstraction, afford cationic [Mn(CO)3(κ 3 P,C,L)](OTf) derivatives exhibiting a meridional or a facial coordinating geometry of tridentate NHC core ligand depending on its relative flexibility. All bi-and tridentate Mn(I) complexes were characterized by X-ray diffraction analysis. The impact of the tridentate ligand structure on catalytic performance was illustrated in the Mn-catalyzed hydrogenation of acetophenone revealing fac-[Mn(CO)3(κ 3 P,C,N)](OTf) based on a 5,6-membered metallacyclic architecture to be the most active, thus evidencing the role of the pyridine arm lability in the catalytic cycle.
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Dates and versions

hal-03128901 , version 1 (02-02-2021)

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Ruqaya Buhaibeh, Carine Guyard-Duhayon, Dmitry A. Valyaev, Jean-Baptiste Sortais, Yves Canac. Cationic PCP and PCN NHC Core Pincer-Type Mn(I) Complexes: From Synthesis to Catalysis. Organometallics, 2021, 40 (2), pp.231−241. ⟨10.1021/acs.organomet.0c00717⟩. ⟨hal-03128901⟩
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