title: Synthesis, characterization and reactivity of new complexes of titanium and zirconium containing a potential tridentate amidinato-cyclopentadienyl ligand.
abstract: Group 4 metal complexes [M(eta(5)-C(5)Me(4)SiMe(2)-eta(1)-N-2R)(NMe(2))(2)] (R = pyridine, pyrazine, pyrimidine, thiazole, M = Ti; R = pyridine, thiazole; M = Zr) containing the tetramethylcyclopentadienyl-dialkylsilyl bridged amidinato as pendant ligand, were synthesized and characterized by elemental analysis, solution (1)H, (13)C and (15)N NMR spectroscopy and experimental (13)C and (15)N CPMAS in the solid state. The crystal structures of [Ti(eta(5)-C(5)Me(4)SiMe(2)-eta(1)-N-2R)(NMe(2))(2)] (R = pyridine, pyrazine, pyrimidine, thiazole) were determined by single crystal X-ray diffraction studies. All compounds exhibit a distorted tetrahedral geometry, with the ansa-monocyclopentadienyl-amido ligands acting in a bidentate mode. The [M(eta(5)-C(5)Me(4)SiMe(2)-eta(1)-N-2R)(NMe(2))(2)] (R = pyridine, thiazole; M = Zr, Ti) complexes are ethylene polymerization catalysts in the presence of MAO and they are active precursors in regioselective catalytic hydroamination operating with an anti-Markovnikov mechanism.
authors.affiliation: Centro di Strutturistica Diffrattometrica, Dipartimento di Chimica, Università di Ferrara, Via Borsari 46, 44100 Ferrara, Italy.
authors.forename: Valerio
authors.initials: V
authors.lastname: Bertolasi
authors.forename: Rita
authors.initials: R
authors.lastname: Boaretto
authors.forename: Michele R
authors.initials: MR
authors.lastname: Chierotti
authors.forename: Roberto
authors.initials: R
authors.lastname: Gobetto
authors.forename: Silvana
authors.initials: S
authors.lastname: Sostero