The Stabilization of Three-Coordinate Formal Mn(0) Complex with NHC and Alkene Ligation

Abstract

We report three-coordinate formal Mn(0) complexes [(NHC)Mn(dvtms)] that have an S = 3/2 ground-spin state and feature highly covalent metal-ligand bonding. These complexes can perform reductive coupling with unsaturated hydrocarbons and show diversified reactivity toward H 2 O, H 2 , CO, and I 2 . The results highlight the synthetic utility of low-coordinate low-valent manganese complexes, warranting further exploration.

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

“…Synthesis of dinuclear Mn (0) complex 159 with bridging ligand 160. Scheme 44) 155. They were prepared via reduction of the corresponding (NHC)MnCl2 adduct by KC8 in the presence of divinyltetramethyldisiloxane.…”

Zeise, Liebig, Jensen, Hückel, Dewar, and the Olefin π‐Complex Bonds

“…[64] Formal Mn 0 diolefin complexes have long CÀCbonds of about 1.38-1.43 . [65] If the interaction between the ethylene p-orbital and metal ion dominates,t he compound is likely to exist as a pcomplex. If metal ion to ethylene-p*b ack-donation is dominant, am etallacyclopropane structure should result.…”

Zeise, Liebig, Jensen, Hückel, Dewar und die Olefin‐π‐Komplex‐Bindung

“…Röntgen‐Strukturdaten für mehrere Verbindungen bestätigen diese Klassifikation . Mn 0 ‐Diolefin‐Komplexe haben lange C‐C‐Bindungen um 1.38–1.43 Å …”

“…[64] Mn 0 -Diolefin-Komplexe haben lange C-C-Bindungen um 1.38-1.43 . [65] Wenn die Wechselwirkung zwischen dem Ethylen-p-Orbital und dem Metallion dominiert, wird die Verbindung wahrscheinlich als p-Komplex vorliegen. Wenn die Metallion-Ethylen-p*-Rückbindung dominiert, sollte eher ein Metallacyclopropan resultieren.…”