Platinum-assisted isomerization of 1-methylenehydrazine into 1-carbenehydrazine.
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.
Köhler
Brigitte
B
Department of Chemistry, Ludwig-Maximilian University of Munich, 81377 Munich, Germany.
Lorenz
Ingo-Peter
IP
Klapötke
Thomas M
TM
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
C553820:1-methylenehydrazine; D006834:Hydrazines; D008024:Ligands; D009944:Organoplatinum Compounds; D010984:Platinum