Reactive cationic dicyclopentadienyl zirconium(IV) complexes

Jordan, Richard F.; Dasher, William E.; Echols, Scott

doi:10.1021/ja00267a068

Cited by 233 publications

(108 citation statements)

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“…174 Cationic [ R Cp2ZrCH3] + zirconocenes have been frequently employed as catalysts in olefin polymerization. 175 As in latetransition metals, the olefin is first inserted into the Zr-CH3 bond and subsequent chain-growth by consecutive olefin insertions takes place. The same has been shown to occur with acetylenes.…”

Section: Elementary Reactions Involving the Tm-ch3 Fragmentmentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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Section: Elementary Reactions Involving the Tm-ch3 Fragmentmentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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“…Shilov and Dyachkovsky, 58 Eisch, 59 Jordan, 60 and Bochmann 61 showed that the activity of metallocene catalysts depends on the formation of cationic species. Today, most research groups agree with this statement.…”

Section: Activation Mechanismmentioning

confidence: 99%

The discovery of metallocene catalysts and their present state of the art

Kaminsky

2004

J. Polym. Sci. A Polym. Chem.

361

221

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Metallocene and other transition metal complexes activated by methylaluminoxane are highly active catalysts for the polymerization of olefins, diolefins, and styrene, which was discovered at the University of Hamburg about 25 years ago. These catalysts allow the synthesis of polymers with a highly defined microstructure, tacticity, and stereoregularity, as well as new copolymers with superior properties such as film clarity, tensile strength, and lower extractables. A better understanding of the mechanism of olefin polymerization leads to findings of other new single site catalysts. The development of the metallocene/MAO-catalysts from their discovery to their present state of the art is presented. Keywords:metallocene catalysts; methylaluminoxane; olefin polymerization; zirconocene complexes; polyolefins; single site catalysis Dr. Kaminsky received his Ph.D. and degree in chemistry from Hamburg University, Germany in 1971 for investigating the side reactions of biscyclopentadienyl-zirconiumdichloride and triethylaluminum. He then served as lecturer and continued his research on the determination of zirconocene/aluminumalkyl-complexes and recycling of polymers by pyrolysis in a fluidized bed process. During that time he and Hansjörg Sinn discovered that the activity of metallocenes and other transition metals can be increased extremely by the addition of MAO as a cocatalyst. In 1979 he became full professor at the University of Hamburg for Technical and Macromolecular Chemistry and has served as director, dean, and president of German chemical society, Hamburg section. Dr. Kaminsky has received the following honors and rewards: elected to the

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“…Cp2Zr(R)+ + CH2C12 -Cp2Zr(R)Cl + "CH2C1+" active inactive (9) "H+" + CpaZr(R)+ » R-H (10) We have observed this type of Cl-abstraction reaction for simple cationic alkyl complexes in the absence of ethylene (eq 11). We are currently in the process of identifying the organic products of this reaction in order to determine the mechanism.…”

Section: Chain Termination and Transfermentioning

confidence: 81%

“…are formed in high yield by the reaction of neutral dialkyl complexes Cp2Zr(R)2 with Ag[BPh4] in CH3CN (eq 4), or with [Cp2Fe] [BPh4] in a variety of solvents (eq 5). To date, R_ = CH3-, Ph", PhCH2" (10)(11)(12). (5) These reactions are believed to proceed by one-electron oxidation of d°C p2Zr(R)2, which occurs with loss of R' radical and formation of Cp2Zr(R)+.…”

Section: Synthesis and Structure Of Cp2zr(r){l)+ Complexesmentioning

confidence: 99%

Introduction

Gladysz¹

1988

J. Chem. Educ.

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Reactive cationic dicyclopentadienyl zirconium(IV) complexes

Cited by 233 publications

References 2 publications

Methyl Complexes of the Transition Metals

Methyl Complexes of the Transition Metals

The discovery of metallocene catalysts and their present state of the art

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