title: Platinum(II) complexes of cyclic triphosphenium ions: a 31P NMR spectroscopic and computational study.
abstract: The first transition metal complexes of cyclic triphosphenium ions have been unequivocally identified in solution by (31)P NMR spectroscopy. The ligands coordinate to platinum(II) via the central phosphorus atom, but only when at least one of the outer phosphorus atoms has non-aromatic substituents. Depending on the system, either trans- (the kinetic reaction product) and/or cis- (the thermodynamic reaction product) complexes are formed. The (1)J coupling constants between (195)Pt and the central phosphorus atom of the CTI (P(A)) are small for both cis- and trans-isomers, between 900 and 1300 Hz, whereas other phosphanes in these complexes derived from the platinum(II) starting material show normal (1)J(PtP) values. These results suggest a possible long P-Pt bond between the overall positively charged ligand and the platinum(II) cation. Calculations including predicted (31)P NMR shifts for the CTIs and their Pt(II) complexes largely support our experimental findings.
authors.affiliation: Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK.
authors.forename: Philippa K
authors.initials: PK
authors.lastname: Coffer née Monks
authors.forename: Robert M K
authors.initials: RM
authors.lastname: Deng
authors.forename: Keith B
authors.initials: KB
authors.lastname: Dillon
authors.forename: Mark A
authors.initials: MA
authors.lastname: Fox
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Olivey
mesh_terms: D009682:Magnetic Resonance Spectroscopy; D009943:Organophosphorus Compounds / Q000737:chemistry*; D009944:Organoplatinum Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010759:Phosphorus Isotopes; D011789:Quantum Theory
chemical_list: D009943:Organophosphorus Compounds; D009944:Organoplatinum Compounds; D010759:Phosphorus Isotopes