Grafting of the zirconium complexes [Zr(η5-C5H5){NC-amidine}Cl2] and [Zr(η5-C5H5)(NC-NacNac)Cl2] and the study of their behavior in ethylene polymerization

• Published in: Journal of molecular catalysis. A, Chemical Vol. 391; pp. 130 - 138
• Main Authors: Cabrera, Alan R., Villaseñor, Elena, Werlinger, Francisca, Rojas, Rene S., Valderrama, Mauricio, Antiñolo, Antonio, Carrillo-Hermosilla, Fernando, Férnadez-Galan, Rafael
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.09.2014; Elsevier
• Subjects: Catalysis; Chemistry; Cyanoamidinate complexes; Ethylene polymerization; Exact sciences and technology; General and physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Zirconium complexes; Ethylene polymerization; Zirconium complexes; Cyanoamidinate complexes; Heterogeneous catalysis; Amidine; Polymerization; Zirconium complex; Grafting
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2014.04.017

New zirconium complexes with pendant CN groups can be coordinated to the acid sites of MAO or inorganic supports, to decrease the required Al/Zr ratio in ethylene polymerization processes. •New zirconium catalyst with pendant CN groups has been synthesized and characterized.•The new zirconium catalyst has been grafted to different inorganic solids.•The nature of the linkage by the CN or the Zr atom has been confirmed by IR studies.•The MAO/Zr ratio required as catalyst for ethylene polymerization is low.•UV–vis has been used to detect the active species. The synthesis of the new zirconium complex [Zr(η5-C5H5){NC-amidine}Cl2] (1) has been achieved by reaction of the amidine (E)-N-(4-cyanophenyl)-N′-(2,6-diisopropylphenyl)acetimidamide with [Zr(η5-C5H5)Cl3] and the new complex has been characterized by spectroscopic methods. The reaction of one equivalent of B(C6F5)3 with compound 1 produces the adduct [Zr(η5-C5H5){(C6F5)3B-NC-amidine}]Cl2 (2). Complexes 1 and 2 have been tested as homogeneous catalysts in olefin polymerization using MAO as cocatalyst. The grafting of 1 and the previously reported complex [Zr(η5-C5H5)(NC-NacNac)Cl2] (3) on to several inorganic solid supports, namely dehydroxylated silica (SiO2(TEMP)) (S1), dehydroxylated silica modified with O(SiMe3)2 (S2) or MAO (S3), and MgCl2 (S4) has been carried out by addition of a freshly prepared solution of 1 or 3 to the corresponding inorganic solid. FT-IR studies of the new materials showed that the links between complexes 1 or 3 and S1 and S2 occur through the zirconium center, whereas with S3 and S4 the links involve the CN functional group of the ligand. These new materials have been studied as catalysts in olefin polymerization reactions in the presence of MAO. A UV–vis study was carried out in order to identify the minimum amount of MAO necessary to produce the active species. A preliminary study into the activity in olefin polymerizations was also carried out.