PDF《Supporting Information》

Supporting Information Synthesis of [(π-Pcyano-nacnac)Cp]and [(π-cyanoP-nacnac)Cp]zirconium Complexes, and their Remote Activation for Ethylene Polymerization Rene S.

Rojas,* ? Alan R. Cabrera,? Brian Peoples,? Mauricio Valderrama,? Kirsten Spannhoff§ , Mauricio Valderrama,a Roland Fr?hlich,§ Gerald Kehr,§ Gerhard Erker* § ? Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile;

§ Chemisches Institut der Universit?t Münster, Corrensstrasse 40,

48149 Münster, Germany. S1 of

23 Experimental Section General Remarks. All manipulations were performed under an inert atmosphere using standard glovebox and Schlenk-line techniques. All reagents were used as received from Aldrich unless otherwise specified. Ethylene was purchased from Matheson Tri- Gas (research grade, 99.99 % pure). Toluene, THF, ether and pentane were distilled from benzophenone ketyl. All polymerization reactions were carried out in a Parr autoclave reactor as described below. Toluene for polymerization was distilled from sodium benzophenone. The following instruments were used for the physical characterization of the compounds. NMR: Varian Inova

500 (1 H:

500 MHz,

13 C:

126 MHz,

19 F:

470 MHz,

11 B:

160 MHz), Bruker Unity Plus

600 (1 H:

600 MHz,

31 C:

151 MHz,

19 F:

564 MHz,

11 B:

64 MHz) and Bruker Advance 400. Most NMR assignments were supported by additional 2D experiments. FT-IR spectra were recorded on a Bruker Vector-22 Spectrophotometer using KBr pellets, and in solution using C6D6 as solvent. X-ray crystal structure analyses: Data sets were collected with a Nonius KappaCCD diffractometer, equipped with a rotating anode generator. Programs used: data collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN (Z. Otwinowski, W. Minor, Methods in Enzymology, 1997, 276, 307-326), absorption correction Denzo (Z.Otwinowski, D. Borek, W. Majewski &

W. Minor, Acta Cryst. 2003, A59, 228-234), structure solution SHELXS-97 (G.M. Sheldrick, Acta Cryst. 1990, A46, 467-473), structure refinement SHELXL-97 (G.M. Sheldrick, Acta Cryst. 2008, A64, 112-122), graphics XP (BrukerAXS, 2000). Graphics show the thermal ellipsoids with

50 % probability, R values are given for the observed reflections, wR2 values for all reflections. S2 of

23 Typical Homopolymerization of Ethylene. Polymerizations were carried out in a Parr autoclave reactor (100 mL), loaded inside a glovebox with an appropriate amount (6.8 μmol) of the pre-catalyst (3, 4,

6 or 7) and the corresponding MAO with toluene, such that the final volume of the toluene solution was

30 mL. The reactor was sealed inside the glovebox (when is indicated, MAO was put into the addition funnel). The reactor was attached to an ethylene line and the gas was fed continuously into the reactor to the pressures of 12.5 bar. The pressurized reaction mixture was stirred at temperature of

75 °C. After

10 min, the ethylene was vented and acetone was added to quench the polymerization. The precipitated polymer was collected by filtration and dried overnight. Polymer Characterization. Polymers were dried overnight under vacuum and the polymerization activities calculated from the mass of product obtained. These values were to within 5% of the calculated mass determined by measuring the ethylene consumed by use of a mass flow controller. The polymers were characterized by Gel Permeation Chromatography (GPC). GPC analysis was performed on a Waters Alliance GPC

2000 system equipped with a refractive index detector. Samples were run at