Synthesis and Structural Diversity of Group 4 Metal Complexes with Multidentate Tethered Phenoxy-Amidine and Phenoxy-Amidinate Ligands

The coordination chemistry of the multidentate tethered amidine-phenol {4,6-tBu2C6H2O­(2-C­(NR)NR}­H2 ({LONR}­H2, R = iPr, 2,6-iPr2C6H3 (Ar)) and new guanidine-phenol {4,6-tBu2C6H2ON­(C6H5)­(2-C­(NR)NR}­H2 ({LON­(Ph)­NiPr}­H2) pro-ligands with group 4 metals has been studied. σ-Bond and salt metathesis reactions were explored to coordinate these (pro)­ligands onto zirconium and hafnium. Alkane elimination reactions between {LONR}­H2 and Zr­(CH2Ph)4 afforded mixed-ligand monobenzyl {LOHNR}­{LONR}­Zr­(CH2Ph) (R = iPr; 1) and monoligand tribenzyl {LOHNAr}­Zr­(CH2Ph)3 (R = Ar; 2) complexes, respectively. Alkane and amine elimination reactions between {LON­(Ph)­NiPr}­H2 and Zr­(CH2Ph)4 or Hf­(NMe2)4 unexpectedly resulted in cleavage of the ligand backbone and eventual isolation of {(Ph)­NC6H2(tBu)2O}­Zr­{(iPrN)2CCH2Ph}2 (3) and {(Ph)­NC6H2(tBu)2O}­Hf­{(iPrN)2CNMe2}2 (4), respectively. Salt metathesis reactions between {LONR}­Li2 and ZrCl4(THF)n (n = 0, 2), conducted in 1:1 ratios, led upon crystallization to diverse chloro complexes: [{LONiPr}­ZrCl]33-O)­(μ3-Cl) (5), [{LONAr}2ZrCl­(μ2-Cl)]2[{LHONAr}­ZrCl­(μ2-Cl)]­(μ3–OH) (6), and {LOHNAr}­ZrCl3(THF) (7). Similar salt metathesis reactions between the monolithium salts {LHONR}Li and ZrCl4, conducted in 2:1 ratios, allowed the selective preparation of bis­(phenoxy-amidine) complexes with pendant amino groups {LOHNR}2ZrCl2 (R = iPr, 8; R = Ar, 9). All complexes were authenticated by elemental analysis, X-ray crystallography, and NMR spectroscopy. Complexes 5, 6, 8, and 9, upon activation with MAO, showed poor to moderate productivities (4–172 (kg of PE) mol–1 h–1) in the polymerization of ethylene, giving linear polymers with large polydispersities.