15191-66-9Relevant academic research and scientific papers
Water as an ideal solvent for the synthesis of easily hydrolyzable compounds: High-yield preparation of 2-pyrrolecarbaldimines and their CVD/ALD-relevant Cu(II) derivatives in H2O
Grushin, Vladimir V.,Marshall, William J.
, p. 1457 - 1460 (2004)
Water was found to be an ideal solvent for the remarkably high-yield, fast preparation of easily hydrolyzable 2-pyrrolecarbaldimines. In the presence of Cu2+, the reaction afforded, in one step, the corresponding Cu(II) chelates which were demonstrated to meet the initial set of current microelectronics criteria for Cu metal deposition via a CVD/ALD process. Electronic effects of the substituent on the imino nitrogen of the Cu complexes were shown to strongly influence the coordination geometry at the Cu center.
Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations
Broomfield, Lewis M.,Sarazin, Yann,Wright, Joseph A.,Hughes, David L.,Clegg, William,Harrington, Ross W.,Bochmann, Manfred
, p. 4603 - 4611 (2008/03/12)
Treatment of MCl3(OC6H3-2-tBu-6-CH{double bond, long}NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN{double bond, long}CHC4H3N]-), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N-O)(N-N). The molecular structures of TiCl2(OC6H3-2-tBu-6-CH{double bond, long}NC6F5)(C2H5N{double bond, long}CHC4H3N) (1c), TiCl2(OC6H3-2-tBu-6-CH{double bond, long}NC6F5)(C6H11N{double bond, long}CHC4H3N) (1b) and ZrCl2(OC6H3-2-tBu-6-CH{double bond, long}NC6F5)(C6H11N{double bond, long}CHC4H3N) (2b) show distorted octahedral geometries with trans-O-,N-/cis-Cl2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene-propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.
Pyrrolide-imine benzyl complexes of zirconium and hafnium: Synthesis, structures, and efficient ethylene polymerization catalysis
Matsui, Shigekazu,Yoshida, Yasunori,Takagi, Yukihiro,Spaniol, Thomas P.,Okuda, Jun
, p. 1155 - 1164 (2007/10/03)
A series of pyrrolyl-imines HL1-6 was prepared by the condensation of pyrrole-2-carboxyaldehyde with different amines. The reaction of 2 equiv of pyrrolyl-imine with tetrabenzyl complexes of hafnium and zirconium M(CH2Ph)4 (M=Hf or Zr) gave dibenzyl complexes (L3-6)2M(CH2Ph) 2, which were characterized by NMR spectroscopy and crystal structure analysis. NMR spectra of the complexes with secondary alkyl substituents at the imine nitrogen (isopropyl: 3a, 4- tert -butylcyclohexyl: 4a and 4b) suggest that rapid racemization between Δ and Λ configurations occurs in solution on the NMR time scale. The complexes with pyrrolide-imine ligands with a tertiary alkyl group such as tert -butyl (5a and 5b) or 1-adamantyl (6a and 6b) at the imine nitrogen possess cis -configured benzyl groups. Hafnium complexes 5a and 6a react with B(C6F5)3 in bromobenzene-d5 to give the corresponding cationic benzyl complexes, which exhibit high activity for ethylene polymerization (5a: 2242 kg-polymer/ mol-Hf h bar, 6a: 2096 kg-polymer/ mol-Hf h bar). Zirconium complexes 5b and 6b display a remarkably high ethylene polymerization activity when activated with methylaluminoxane (5b: 17,952 kg-polymer/mol-Zr h bar, 6b: 22,944 kg-polymer/mol-Zr h bar).
