Platinum Stilbazoles: Ring-Walking Coupled with Aryl−Halide Bond Activation
- 10 June 2005
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (26) , 9322-9323
- https://doi.org/10.1021/ja050613h
Abstract
The reaction between tetrakis(triethylphosphine)platinum(0) and 4-[trans-2-(4-bromophenyl)vinyl]pyridine (1) is examined. Initially, the metal center coordinates to the bridging double bond of 1. Complexes 2 and 3 were fully characterized, and their X-ray crystallography structures are presented. Upon heating, either in solution or in the solid state, complex 2 undergoes C-Br oxidative addition to give complex 3. Kinetic studies revealed that this conversion is unimolecular and does not involve dissociation of the metal center from the double bond. Density functional studies show that a plausible mechanism involves the metal center "walking" around the pi-system from the bridging C=C double bond to the C-Br bond.Keywords
This publication has 20 references indexed in Scilit:
- A New Generation of π-Basic Dearomatization AgentsOrganometallics, 2005
- Development of density functionals for thermochemical kineticsThe Journal of Chemical Physics, 2004
- Arene Hapticity in (C6H6)Cr(CO)n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy SurfacesOrganometallics, 2004
- η2-Coordination and C−H Activation of Electron-Poor ArenesOrganometallics, 2002
- A pyracylene model for the interaction of transition metals with fullerenes: a density functional studyJ. Chem. Soc., Dalton Trans., 2002
- Kinetic and Mechanistic Study of the Displacement of η2-Coordinated Arenes from Cp*Re(CO)2(η2-C6H5R) (R = H, CH3, C(CH3)3): Evidence for a Dissociative Mechanism and Estimation of the Re−(η2-Arene) Bond StrengthOrganometallics, 2001
- Substituent effects on .eta.2-coordinated arene complexes of pentaammineosmium(II)Journal of the American Chemical Society, 1988
- A .eta.2-arene complex of rhenium: synthesis, characterization, and activation of the aromatic carbon-hydrogen bondsOrganometallics, 1983
- Preparation and reactions of triethylphosphine complexes of zerovalent nickel, palladium, and platinumInorganic Chemistry, 1976
- Kinetics and Mechanism of Substitution Reactions of Arene Molybdenum TricarbonylJournal of the American Chemical Society, 1966