title: Synthesis, structures, and norbornene polymerization behavior of C(sp³), N-chelated palladacycles bearing o-aryloxide-N-heterocyclic carbene ligands.
abstract: Treatment of the o-hydroxyaryl imidazolium pro-ligands (2-OH-3,5-tBu2C6H2)(R)(C3H3N2)(+)Br(-) [R = Mes (1a), Ph (1b), iPr (1c), Me (1d)] with Ag2O afforded the corresponding silver complexes 2a-d. Subsequent metal-exchange reactions of 2a-d with [Pd(OAc)(8-Me-quin-H)]2 (3) yielded the desired C(sp(3)), N-chelated and o-aryloxide-NHC-ligated palladacycle complexes 4a-d in 60-80% yields. When the N-tert-butyl substituted o-hydroxyaryl imidazolium pro-ligand 1e reacted with 3 in the presence of K2CO3 in dioxane, the palladacycle complex 4e, in which the NHC adopted an abnormal binding (C4-bonding), was obtained in 20% yield. All these complexes were fully characterized using (1)H and (13)C NMR spectra, high-resolution mass spectrometry (HRMS), and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures of 4a-c and the abnormal binding of NHC in 4e. With methylaluminoxane (MAO) as the cocatalyst these palladacycles showed excellent catalytic activities of up to 10(7) g of PNB (mol of Pd)(-1) h(-1) in the addition polymerization of norbornene.
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China. bqwang@nankai.edu.cn.
authors.forename: Liang
authors.initials: L
authors.lastname: Dang
authors.forename: Jing
authors.initials: J
authors.lastname: Guo
authors.forename: Haibin
authors.initials: H
authors.lastname: Song
authors.forename: Binyuan
authors.initials: B
authors.lastname: Liu
authors.forename: Baiquan
authors.initials: B
authors.lastname: Wang