title: Metal-ligand cooperation in H2 activation with iron complexes bearing hemilabile bis(diphenylphosphino)amine ligands.
abstract: The octahedral transition-metal complex [(dppa)Fe(Ph2P-N-PPh2)2] (1) [dppa = bis(diphenylphosphino)amine] with homofunctional bidentate ligands is described. The ligand exhibits hemilability due to its small bite angle and the steric repulsion of the coordinated donor groups. As the {Ph2P-N-PPh2}(-) ligand can act as an internal base, heterolytic cleavage of dihydrogen by complex 1 leads to the formation of the hydride complex [(dppa)(Ph2P-N-PPh2)Fe(H)(κ(1)-Ph2P-NH-PPh2)2] (2), representing an example of cooperative bond activation with a homofunctional hemilabile ligand. This study demonstrates that hemilability of homofunctionalized ligands can be affected by careful adjustment of geometric parameters.
authors.affiliation: Department of Chemistry, Philipps-Universität Marburg , Hans-Meerwein-Str., 35043 Marburg, Germany.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Frank
authors.forename: Katharina
authors.initials: K
authors.lastname: Hanau
authors.forename: Robert
authors.initials: R
authors.lastname: Langer
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*
chemical_list: D000814:Aniline Compounds; D005296:Ferrous Compounds; D008024:Ligands; D010720:Phosphines; C581478:bis(diphenylphosphino)amine; D006859:Hydrogen