TY - JOUR
T1 - 4,4′-Biphenolate complexes of titanium and zirconium
AU - Barnes, Denise L.
AU - Eilerts, Nancy W.
AU - Heppert, Joseph A.
N1 - Funding Information:
Acknowledgements-Weth ank the Donors of the Petroleum ResearchF und administeredb y the American ChemicalS ocietyf or partial support of this work. Part of this materiali s also basedo n work supportedb y the National ScienceF oundation under EPSCoR grant no. OSR-9255223T. he governmentr etainsc ertain rights in this material.
PY - 1994
Y1 - 1994
N2 - 4,4′-Biphenolate ligands (R4BIPOH2) bearing methyl or tert-butyl substituents in the 3,3′,5,5′-positions participate in alcoholysis reactions with metal precursors, including TiCl4, Ti(OiPr)4 and Cp2MCl2. The tetra-tert-butyl derivative shows evidence of an intermediate monotitanium species (Bu4BIPOH)Ti(OiPr)3 during titrations of the ligand with Ti(OiPr)4, while (Bu4BIPO)(TiOiPr)3)2 exists as a simple monomeric molecule in solution. (Me4BIPO)(Ti(OiPr)3)2 shows evidence of aggregation into oligomeric species in solution, although its insolubility hampered the complete characterization of these species. A reaction between the d1 complex TiCl3(THF)3 and 3,3′,5,5′-tBu4-4,4′-biphenoquinone produced (Bu4BIPO)[TiCl3(THF)]2, while dirct reactions between TiCl4 and Bu4BIPOH2 in toluene resulted in the isolation of the dealkylated product, (Bu2BIPO)[TiCl3(Et2O)]2 (where the tBu groups occur in the 3,3′-positions), after treatment with ether. Refluxing Me4BIPOH2 and Cp2MCl2 (M = Ti or Zr) in toluene produced bismetallocene chloride complexes.
AB - 4,4′-Biphenolate ligands (R4BIPOH2) bearing methyl or tert-butyl substituents in the 3,3′,5,5′-positions participate in alcoholysis reactions with metal precursors, including TiCl4, Ti(OiPr)4 and Cp2MCl2. The tetra-tert-butyl derivative shows evidence of an intermediate monotitanium species (Bu4BIPOH)Ti(OiPr)3 during titrations of the ligand with Ti(OiPr)4, while (Bu4BIPO)(TiOiPr)3)2 exists as a simple monomeric molecule in solution. (Me4BIPO)(Ti(OiPr)3)2 shows evidence of aggregation into oligomeric species in solution, although its insolubility hampered the complete characterization of these species. A reaction between the d1 complex TiCl3(THF)3 and 3,3′,5,5′-tBu4-4,4′-biphenoquinone produced (Bu4BIPO)[TiCl3(THF)]2, while dirct reactions between TiCl4 and Bu4BIPOH2 in toluene resulted in the isolation of the dealkylated product, (Bu2BIPO)[TiCl3(Et2O)]2 (where the tBu groups occur in the 3,3′-positions), after treatment with ether. Refluxing Me4BIPOH2 and Cp2MCl2 (M = Ti or Zr) in toluene produced bismetallocene chloride complexes.
UR - http://www.scopus.com/inward/record.url?scp=0347998906&partnerID=8YFLogxK
U2 - 10.1016/S0277-5387(00)81678-2
DO - 10.1016/S0277-5387(00)81678-2
M3 - Article
AN - SCOPUS:0347998906
SN - 0277-5387
VL - 13
SP - 743
EP - 748
JO - Polyhedron
JF - Polyhedron
IS - 5
ER -