Palladium-catalyzed arylation of bis(4-bromo-2-methylinden-1-yl)dimethylsilane and related compounds

Abstract

A new procedure was developed for the synthesis of a broad range of ansa zirconocenes containing bis(2 methyl 4 arylindenyl)dimethylsilane ligands. The method is based on the palladium catalyzed reaction of halogen substituted bis(indenyl)dimethylsilanes with various organozinc compounds. The aryl substituted bridging ligands thus prepared serve as the starting compounds for the synthesis of ansa zirconocenes, which can be used as components of promising catalysts for propylene polymerization. (4 bromo 2 methylinden 1 yl)dimethylsilane.Recent extensive research into the relationship be tween the structures of ansa metallocenes and the activity and stereoselectivity of the corresponding catalysts for propylene polymerization showed that the best results were achieved for catalysts based on the so called improved ansa zirconocenes A containing bis(2 methyl 4 aryl indenyl)dimethylsilane ligands, as well as on related com plexes B containing 3 aryl 2,5 dimethylcyclopenta[b] thienyl moieties.

Connection of Stereoselectivity, Regioselectivity, and Molecular Weight Capability in rac-R′2Si(2-Me-4-R-indenyl)2ZrCl2 Type Catalysts

“…19,20 ■ EXPERIMENTAL SECTION Catalyst Synthesis. The precursor compounds 4-bromo-1methoxy-2-methylindane, 21 bis(4-bromo-2-methyl-1H-inden-1-yl)dimethylsilane, bis(4-chloro-2-methyl-1H -inden-1-yl)dimethylsilane, 22 and Zr[PhN(CH 2 ) 3 NPh]Cl 2 (THF) 2 , 23 metallocenes M6 and M17, 24 M4, 21 M8, 25 M7, M9, M10, and M13, 26 and M11, M14, and M15 27 were synthesized according to the literature. 28 The synthesis of M3, M5, M12, M16, M18, and M19 is detailed in the Supporting Information.…”

An Integrated High Throughput Experimentation/Predictive QSAR Modeling Approach to ansa-Zirconocene Catalysts for Isotactic Polypropylene

“…Details for the synthesis of M20 - M28 , M31 - M36, and M39-M43 , including Figures S1–S38 with 1 H-NMR (odd numbers) and 13 C-NMR (even numbers). Additional references relevant for synthesis [ 58 , 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 , 113 , 114 , 115 , 116 ]. Detailed polymerization procedure and results (Table S1: Propene Polymerization Experiments, Table S2: Full Polymer Characterization, Table S3: Performance of selected catalysts when activated with MAO).…”