title: Platinum-assisted isomerization of 1-methylenehydrazine into 1-carbenehydrazine.
abstract: This theoretical study addresses the experimentally known fact that the ligand system 1-(2-(diphenylphosphino)benzylidene)-2-phenylhydrazine (L) coordinates to palladium centers via the N atom as a 1-methylenehydrazine ligand. In the case of platinum, a 1,2-H shift occurs, and a coordination via the C atom of the newly formed 1-carbenehydrazine ligand is observed. DFT calculations show that the free 1-methylenehydrazine ligand is favored over the free 1-carbenehydrazine ligand by ca. 42 kcal mol(-1). Coordination to a metal center, however, lowers this energy difference to ca. 8-14 kcal mol(-1) in the case of Pd and to essentially zero for Pt.
authors.affiliation: Department of Chemistry, Ludwig-Maximilian University of Munich, 81377 Munich, Germany.
authors.forename: Brigitte
authors.initials: B
authors.lastname: Köhler
authors.forename: Ingo-Peter
authors.initials: IP
authors.lastname: Lorenz
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Klapötke
mesh_terms: D002384:Catalysis; D003198:Computer Simulation; D006834:Hydrazines / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C553820:1-methylenehydrazine; D006834:Hydrazines; D008024:Ligands; D009944:Organoplatinum Compounds; D010984:Platinum