title: Pd(II) and Pt(II) complexes of 2-(2'-pyridyl)-4,6-diphenylphosphinine: synthesis, structure, and reactivity.
abstract: The coordination chemistry of the bidentate P,N hybrid ligand 2-(2'-pyridyl)-4,6-diphenylphosphinine (1) towards Pd(II) and Pt(II) has been investigated. The molecular structures of the complexes [PdCl(2)(1)] and [PtCl(2)(1)] were determined by X-ray diffraction, representing the first crystallographically characterized λ(3)-phosphinine-Pd(II) and -Pt(II) complexes. Both complexes reacted with methanol at the P=C double bond at an elevated temperature, leading to the corresponding products [MCl(2)(1H·OCH(3))]. The molecular structure of [PdCl(2)(1H·OCH(3))] was determined crystallographically and revealed that the reaction with methanol proceeds selectively by syn addition and exclusively to one of the P=C double bonds. Strikingly, the reaction of [PdCl(2)(1H·OCH(3))] with the chelating diphosphine DPEphos at room temperature in CH(2)Cl(2) led quantitatively to [PdCl(2)(DPEphos)] and phosphinine 1 by elimination of CH(3)OH and rearomatization of the phosphorus heterocycle.
authors.affiliation: Department of Chemical Engineering and Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.
authors.forename: Ariadna
authors.initials: A
authors.lastname: Campos-Carrasco
authors.forename: Leen E E
authors.initials: LE
authors.lastname: Broeckx
authors.forename: Jarno J M
authors.initials: JJ
authors.lastname: Weemers
authors.forename: Evgeny A
authors.initials: EA
authors.lastname: Pidko
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.forename: Anna M
authors.initials: AM
authors.lastname: Masdeu-Bultó
authors.forename: Dieter
authors.initials: D
authors.lastname: Vogt
authors.forename: Christian
authors.initials: C
authors.lastname: Müller
mesh_terms: D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C556846:2-(2'-pyridyl)-4,6-diphenylphosphinine; D010720:Phosphines; D011725:Pyridines; D010984:Platinum; D010165:Palladium