Metal

Catalysis

Valence (chemistry)

Polymer chemistry

Phosphine

Ketone

Photochemistry

Receptor

Ylide

Biochemistry

Inorganic chemistry

Deprotonation

Stereochemistry

Medicinal chemistry

Ligand (biochemistry)

Organic chemistry

Phosphonium

Manganese

Hydride

Crystallography

Chemistry

Angewandte Chemie International Edition

Deprotonation of the MnI NHC-phosphine complex fac-[MnBr(CO)3 (κ2 P,C-Ph2 PCH2 NHC)] (2) under a H2 atmosphere readily gives the hydride fac-[MnH(CO)3 (κ2 P,C-Ph2 PCH2 NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)3 (κ3 P,C,C-Ph2 PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)3 (κ2 P,C-Ph2 P=CHNHC)] (6 b) as key intermediate able to activate H2 via a non-classical mode of metal-ligand cooperation implying a formal λ5 -P-λ3 -P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200).

Phosphine‐NHC Manganese Hydrogenation Catalyst Exhibiting a Non‐Classical Metal‐Ligand Cooperative H<sub>2</sub> Activation Mode

Phosphine‐NHC Manganese Hydrogenation Catalyst Exhibiting a Non‐Classical Metal‐Ligand Cooperative H2 Activation Mode

Phosphine‐NHC Manganese Hydrogenation Catalyst Exhibiting a Non‐Classical Metal‐Ligand Cooperative H₂ Activation Mode