121115-33-1Relevant articles and documents
Ligand Control of Agostic M...H...C Three-centre, Two-electron Bonding in Bicyclohept-2-yl Complexes of Platinum and Palladium. X-Ray Crystal Structures of 2-C7H10)(But2P(CH2(2PBut2)> and t2P(CH2)2PBut2)>
Carr, Nicholas,Dunne, Barry J.,Mole, Laura,Orpen, A. Guy,Spencer, John L.
, p. 863 - 871 (1991)
The reaction of non-co-ordinating acids with the Pt0 and Pd0 alkene complexes 2-C7H10)(L-L)> t2P(CH2)2PBut2, 1b or 1g; and o-C6H4(CH2PBut2)2, 11e or 1h; M = Pt, L-L = (C6H11)2P(CH2)2P(C6H11)2 1c or But2P(CH2)2PBut2 1d> affords a series of cationic bicyclohept-2-yl complexes 2a-2h in which the otherwise electron-deficient metal centre is stabilized by a three-centre two-electron (agostic) interaction with the exo-3-CH bond.The complexes were characterized by 1H, 13C and 31P NMR spectroscopy and for 1b and 2b by single-crystal x-ray crystallography.In complex 1b the norborn-2-ene is bound to the platinum in a normal in-plane η2-mode with equal Pt-C distances and Pt-P distances y2.273(2), 2.274(2) Angstroem>.For 2b the crystallographic results reveal a long Pt-Cβ contact of 2.309(5) Angstroem which is bridged by a hydrogen atom forming the agostic bond, whereas the Pt-Cα bond is shortened to 2.096(4) Angstroem.The Pt-P bond trans to the weak agostic bond is significantly shorter than the cis Pt-P bond , and this asymmetry in the co-ordination of the diphosphine is reflected in the 31P NMR spectrum of 2b for which 1J(PtPtrans) >>> 1J(ptPcis).The extent of agostic interaction, as indicated by NMR parameters 1J(ptH), 1J(PtPtrans), etc.>, depends on the bite angle of the diphosphine and the bulk of the substituents on phosphorus such that the smallest diphosphines induce the strongest M...H...C interaction.All the agostic complexes undergo a rapid intramolecular rearrangement on the NMR time-scale at room temperature involving β-elimination and alkene rotation.However, the 31P nuclei remain non-equivalent up to 300 K.
Catalytic oxidation of alcohol via nickel phosphine complexes with pendant amines
Weiss, Charles J.,Das, Parthapratim,Miller, Deanna L.,Helm, Monte L.,Appel, Aaron M.
, p. 2951 - 2958 (2015/02/19)
Nickel complexes were prepared with diphosphine ligands that contain pendant amines, and these complexes catalytically oxidize primary and secondary alcohols to their respective aldehydes and ketones. Kinetic and mechanistic studies of these prospective electrocatalysts were performed to understand what influences the catalytic activity. For the oxidation of diphenylmethanol, the catalytic rates were determined to be dependent on the concentration of both the catalyst and the alcohol and independent of the concentration of base and oxidant. The incorporation of pendant amines to the phosphine ligand results in substantial increases in the rate of alcohol oxidation with more electron-donating substituents on the pendant amine exhibiting the fastest rates. (Chemical Equation Presented).