Bis[diphenylphosphino]methane and its bridge-substituted analogues as chemically non-innocent ligands for H₂ activation

Abstract

Interconversion between coordinated diphosphinomethane and diphosphinomethanide moieties can be used as a new tool for metal–ligand cooperation.

Manganese Diphosphine and Phosphinoamine Complexes Are Effective Catalysts for the Production of Biofuel Alcohols via the Guerbet Reaction

“…Given the importance of ligand-assisted mechanisms in hydrogen transfer catalysis, our working hypothesis is that involvement of the acidic hydrogens in the methylene backbone of dppm may be important; recent reports in related chemistry support this hypothesis. 25,36,37 A recent paper by Kireev et al supports our hypothesis of dppm acting as a noninnocent ligand on manganese. 36 In this paper, monochelate 7 is reacted with KHMDS to form complex 7b, containing two highly strained 3-membered rings.…”

“…Given the importance of ligand-assisted mechanisms in hydrogen transfer catalysis, our working hypothesis is that involvement of the acidic hydrogens in the methylene backbone of dppm may be important; recent reports in related chemistry support this hypothesis. 25 , 36 , 37 …”

“…A recent paper by Kireev et al supports our hypothesis of dppm acting as a noninnocent ligand on manganese. 36 In this paper, monochelate 7 is reacted with KHMDS to form complex 7b , containing two highly strained 3-membered rings. This can then be converted to hydride complex 7c under 50 atm of hydrogen ( Scheme 4 ).…”

“…It is not clear why dppm remains the most effective ligand for isobutanol production with both manganese and ruthenium. Given the importance of ligand-assisted mechanisms in hydrogen transfer catalysis, our working hypothesis is that involvement of the acidic hydrogens in the methylene backbone of dppm may be important; recent reports in related chemistry support this hypothesis. ,, …”

Iron Dual-atom Catalyst combine with ″vicinal nonmetallic sites″ for efficient Ammonia Synthesis

“…The *H stabilized by the electron-de cient B atom (as Lewis acid) will change the transfer order of *H on supports acting as a noninnocent ligand in homogenous catalysis. 55,56 In the Fe 2 /B/mpg-C 3 N 4 , *H on the B site would preferentially transfer to the Fe1 site with an energy barrier of 0.75eV and continue to attack the activated *N 2 to form the *N 2 H intermediate. After that, the *H on the N1 site will shift to the Fe1 site via a 0.86eV barrier that is slightly higher energy compared to that in the Fe 2 /mpg-C 3 N 4 system (0.75eV).…”