title: Synthesis of Carboxylate Cp*Zr(IV) Species: Toward the Formation of Novel Metallocavitands.
abstract: With the intent of generating metallocavitands isostructural to species [(CpZr)3(μ(3)-O)(μ(2)-OH)3(κO,O,μ(2)-O2C(R))3](+), the reaction of Cp*2ZrCl2 and Cp*ZrCl3 with phenylcarboxylic acids was carried out. Depending on the reaction conditions, five new complexes were obtained, which consisted of Cp*2ZrCl(κ(2)-OOCPh) (1), (Cp*ZrCl(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2 (2), [(Cp*Zr(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2(μ(2)-OH)2]·Et2O (3·Et2O), [[Cp*ZrCl2](μ-Cl)(μ-OH)(μ-O2CC6H5)[Cp*Zr]]2(μ-O2CC6H5)2 (4), and [Cp*ZrCl4][(Cp*Zr)3(κ2-OOC(C6H4Br)3(μ3-O)(μ2-Cl)2(μ2-OH)] [5](+)[Cp*ZrCl4](-). The structural characterization of the five complexes was carried out. Species 3·Et2O exhibits host-guest properties where the diethyl ether molecule is included in a cavity formed by two carboxylate moieties. The secondary interactions between the cavity and the diethyl ether molecule affect the structural parameters of the complex, as demonstrated be the comparison of the density functional theory models for 3 and 3·Et2O. Species 5 was shown to be isostructural to the [(CpZr)3(μ(3)-O)(μ(2)-OH)3(κO,O,μ(2)-O2C(R))3](+) metallocavitands.
authors.affiliation: †Département de Chimie, ‡Centre de Recherche sur les Matériaux Avancés (CERMA), and §Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada, G1V 0A6.
authors.forename: Maxime
authors.initials: M
authors.lastname: Daigle
authors.affiliation: †Département de Chimie, ‡Centre de Recherche sur les Matériaux Avancés (CERMA), and §Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada, G1V 0A6.
authors.forename: Wenhua
authors.initials: W
authors.lastname: Bi
authors.affiliation: †Département de Chimie, ‡Centre de Recherche sur les Matériaux Avancés (CERMA), and §Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada, G1V 0A6.
authors.forename: Marc-André
authors.initials: MA
authors.lastname: Légaré
authors.affiliation: †Département de Chimie, ‡Centre de Recherche sur les Matériaux Avancés (CERMA), and §Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada, G1V 0A6.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Morin
authors.affiliation: †Département de Chimie, ‡Centre de Recherche sur les Matériaux Avancés (CERMA), and §Centre de Catalyse et Chimie Verte (C3V), Université Laval, 1045 Avenue de la Médecine, Québec, Québec, Canada, G1V 0A6.
authors.forename: Frédéric-Georges
authors.initials: FG
authors.lastname: Fontaine
mesh_terms: D002264:Carboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry*; D002712:Chlorides / Q000138:chemical synthesis / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015040:Zirconium / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D002712:Chlorides; D056831:Coordination Complexes; D015040:Zirconium; C429984:zirconium chloride