Metal catalysts for the vinyl/addition polymerization of norbornene

The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-t...

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands.

Four new dinuclear Ni/Mn model complexes RN(PPh2)2Ni(μ-SEt)2(μ-Cl)Mn(CO)3 (7, R = p-MeC6H4CH2; 8, R = EtO2CCH2) and RN(PPh2)2Ni(μ-SEt)2(μ-Br)Mn(CO)3 (9, R = p-MeC6H4CH2; 10, R = EtO2CCH2) have been prepared via the four separated step-reactions involving six new precursors RN(PPh2)2 (1, R = p-MeC6H4CH2; 2, R = EtO2CCH2), RN(PPh2)2NiCl2 (3, R = p-MeC6H4CH2; 4, R = EtO2CCH2), and RN(PPh2)2Ni(SEt)2 (5, R = p-MeC6H4CH2; 6, R = EtO2CCH2). The Et3N-assisted aminolysis of Ph2PCl with p-MeC6H4CH2NH2 or EtO2CCH2NH2·HCl in CH2Cl2 gave the azadiphosphine ligands 1 and 2 in 38% and 53% yields, whereas the coordination reaction of 1 or 2 with NiCl2·6H2O in CH2Cl2/MeOH afforded the mononuclear Ni dichloride complexes 3 and 4 in 59% and 78% yields, respectively. While thiolysis of 3 or 4 with EtSH under the assistance of Et3N in CH2Cl2 produced the mononuclear Ni dithiolate complexes 5 and 6 in 64% and 68% yields, further treatment of 5 and 6 with Mn(CO)5Cl or Mn(CO)5Br resulted in formation of the dinuclear Ni/Mn model...

Synthesis, structural characterization, and electrochemical properties of dinuclear Ni/Mn model complexes for the active site of [NiFe]-hydrogenases.

Several N-functionalized bis(phosphanyl)amine ligands respectively containing benzyl, furfuryl, thiophene-2-methyl, thiophene-2-ethyl, and 2-picolyl groups (1a–e) were synthesized and characterized. The ligands reacted with (DME)NiBr2 in CH2Cl2 to give their corresponding nickel complexes [Ph2PN(R)PPh2NiBr2] [R = CH2C6H5 (2a), CH2C4H3O (2b), CH2C4H3S (2c), CH2C5H4N (2d), and CH2CH2C4H3S (2e)]. The structures of these complexes were established by single-crystal X-ray crystallography. All these nickel complexes were highly active towards ethylene oligomerization in the presence of methylaluminoxane or Et2AlCl, producing a high content of butene (C4). Especially for 2e, which contains a thiophene-2-ethyl pendant group, the oligomerization products obtained at –40 °C contained 95.9 mol-% C4 fraction with 100 mol-% 1-butene. Over 50 °C, however, these nickel complexes underwent Friedel–Crafts alkylation of toluene with ethylene and the olefin oligomers.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Syntheses, Structures, and Catalytic Ethylene Oligomerization Behaviors of Bis(phosphanyl)aminenickel(II) Complexes Containing N‐Functionalized Pendant Groups

Synthesis and characterizations of N,N,N′,N′-tetrakis (diphenylphosphino)ethylendiamine derivatives: Use of palladium(II) complex as pre-catalyst in Suzuki coupling and Heck reactions

A new diphosphinoamine ligand [Ph2PN(p-C6H4OMe)PPh2] was prepared through aminolysis reaction of p-methoxyaniline with Ph2PCl in the presence of NEt3. Consequently, the corresponding nickel (II) diphosphinoamine complex [(p-C6H4OMe)N(PPh2)2NiCl2] was synthesized and characterized. The solid-state structure of the complex was determined by single-crystal X-ray diffraction. As combined with methylaluminoxane (MAO), the complex displayed high catalytic activity for vinyl polymerization of norbornene. Copyright © 2005 John Wiley & Sons, Ltd.

Vinyl polymerization of norbornene with novel nickel (II) diphosphinoamine/methylaluminoxane catalytic system

Herein, six new [Cu(N^N)(P^P)]+/0 complexes with different N-ligand and counteranions [Cu2(dmp)2(bdppmapy)I2] (1), [Cu2(dmp)2(bdppmapy)(CN)2]·3CH3OH (2), [Cu(dmp)(bdppmapy)](BF4) (3), [Cu(dmp)(bdppmapy)](ClO4) (4), [Cu(phen)(bdppmapy)](BF4) (5), [Cu(phen)(bdppmapy)](ClO4) (6) have been synthesized and characterized (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine,...

Designing luminescent diimine-Cu (I)-phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

Abstract Two copper(I) complexes, [Cu(bdppmapy)(BTZ)]BF4 (1) and [Cu(bdppmapy)(BTZ)]ClO4 (2) (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine, BTZ = 2,2-bithiazole), have been synthesized in mixed CH3OH and CH2Cl2 (1:1, V/V) and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H NMR and 31P NMR spectroscopy, fluorescence spectra and terahertz time-domain spectroscopy (THz-TDS). Complex 1, a mononuclear complex, was generated by the reaction of [Cu(CH3CN)4]BF4 and bdppmapy with BTZ in a 1:1:1 molar ratio. In 1, the center Cu(I) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and N-ligands BTZ. Complex 2 was obtained by reacting [Cu(CH3CN)4]ClO4 and bdppmapy with BTZ in a 1:1:1 molar ratio. In 2, the bdppmapy and BTZ ligands chelate Cu(I). Luminescent spectra show that the emission mechanism is ascribed to metal-to-ligand charge transfer (MLCT). Terahertz time-domain spectroscopy was also used to characterize these two complexes. Graphical Abstract

Synthesis, spectral properties and terahertz time domain spectroscopy of two copper(I) complexes based on bisphosphine and bisazo ligands

Herein, a series of ionic mononuclear Cu(I) complexes, [Cu(phen)(bdppmapy)]Cl (1a), [Cu(phen)(bdppmapy)]Br (2a), [Cu(phen)(bdppmapy)]I (3a), [Cu(phen)(bdppmapy)]SCN (4a), [Cu(Dpq)(bdppmapy)]Cl (1b), [Cu(Dpq)(bdppmapy)]Br (2b), [Cu(Dpq)(bdppmapy)]I (3b) and [Cu(Dpq)(bdppmapy)]SCN (4b) {phen = [1,10]phenanthroline; Dpq =...

Zhengguang Sun

Papers

Vinyl polymerization of norbornene with novel nickel (II) diphosphinoamine/methylaluminoxane catalytic system

Designing luminescent diimine-Cu (I)-phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

Synthesis, spectral properties and terahertz time domain spectroscopy of two copper(I) complexes based on bisphosphine and bisazo ligands

Study on the influence conditions of luminescence properties of ionic [Cu(N^N)(P^P)]+ complexes: ligands, counteranions and weak interactions