Reactions of Unsaturated Compounds

Kaminsky, Werner; Arndt‐Rosenau, Michael

doi:10.1002/9783527618231.ch2c

Cited by 8 publications

(9 citation statements)

References 427 publications

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“…In cyclopentene polymerization no cis-I ,2 enchainment is observed indicating that the approach of a second monomer is forbidden. A situation similar to the ones described above is reached if the polymerization of propene is conducted at very low monomer concentrations [23,24].…”

Section: Resultssupporting

confidence: 59%

Polymerization with metallocene catalysts. Hydrooligomerization and NMR investigations concerning the microstructure of poly(cyclopentenes)

Arndt

Kaminsky

1995

Macromolecular Symposia

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I -21: Hydrooligomerizations and polymerizations of cyclopentene were carried out using Cs, Cz and CpV symmetric zirconocenes and methylaluminoxane as catalyst. The structure of the hydrotrimers was investigated by one-and twodimensional NMR spectroscopy and correlated to the structure of the polymers. The assignments for the 13C-NMR spectrum of the cis-I ,3-enchained hydrotrimer made by Collins [3] are corrected. Cis-I ,3-enchainment of the configurational base units in the poly(cyc1opentenes) is confirmed. rac-[MezSi( Ind)z]ZrClz I M A 0 catalysis features crystalline polymers and the erythrodiisotactic hydrotetramer indicating highly stereoselective insertion. CpzZrCln / M A 0 and [Ph~C(Fluo)(Cp)]ZrCl2 / M A 0 show none or low stereoselectivity respectively yielding amorphous polymers and both of the diastereomeric hydrotetramers.

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Section: Resultssupporting

confidence: 59%

Polymerization with metallocene catalysts. Hydrooligomerization and NMR investigations concerning the microstructure of poly(cyclopentenes)

Arndt

Kaminsky

1995

Macromolecular Symposia

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“…15 Among them, C 4 , C 6 , and C 8 aolefins are the most valuable compounds in terms of applications, 16 and the oligomerization of ethylene represents one of the easiest and most promising ways to produce them. Titaniumbased Ziegler-Natta systems 17 are certainly the most widespread catalysts for this transformation, but some other approaches have been developed over the last decade, such as those based, for instance, on nickel catalysts. 14,18,19 These last systems show an excellent activity (more than 90% of butene and turn-over frequencies superior to 60,000 mol[C 2 H 4 ]mol [Ni] 21 h…”

Section: The Analyzed Catalytic Reactionmentioning

confidence: 99%

How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study

Tognetti¹,

Floch²,

Adamo³

2009

J Comput Chem

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In this article, we present a critical study of the theoretical protocol used for the determination of the nickel(II) catalyzed ethylene dimerization mechanism, considered as a representative example of the various problems related to the modeling a catalytic cycle. The choice of an appropriate computational procedure is indeed crucial for the validity of the conclusions that will be drawn from the computational process. The influence of the exchange-correlation functional on energetic profiles and geometries, the role of the basis set describing the metal atom, as well as the importance of the chosen molecular model, have been thus examined in details. From the obtained results, some general conclusions and guidelines are presented, which could constitute useful warnings in modeling homogenous catalysis. Besides, the database constituted by our high-level calculations can be used within benchmarking procedures to assess the performances of new computational methods based on density functional theory.

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“…Primary alkyl chloride ( 21–22 ) and bromide ( 23 ) substrates performed well, demonstrating remarkable selectivity of this catalyst for Si–Cl over C–halide activation and allowing further reactivity such as substitution and cross-coupling reactions. 16c, 32 In contrast to our previously published silyl-Negishi reaction, 11 synthetically useful terminal alkenes 33 ( 24 ) also progressed without incident. Aryl substitution such as pentafluoroaryl ( 25 ), biphenyl ( 26 ), and phenyl ether ( 27 ) substrates were well tolerated.…”

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confidence: 94%

Palladium-Catalyzed Cross-Coupling of Monochlorosilanes and Grignard Reagents

2017

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Using a palladium catalyst supported by DrewPhos, the alkylation of monochlorosilanes with primary and secondary alkyl-magnesium halides is now possible. Arylation with sterically demanding aromatic magnesium halides is also enabled. This transformation overcomes the high bond strength of the Si–Cl bond (113 kcal/mol) and is a rare example of a transition-metal catalyzed process involving its activation. Due to the availability of both chlorosilanes and organomagnesium halide reagents, this method allows for the preparation of a wide range of alkyl and aryl silanes.

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Reactions of Unsaturated Compounds

Cited by 8 publications

References 427 publications

Polymerization with metallocene catalysts. Hydrooligomerization and NMR investigations concerning the microstructure of poly(cyclopentenes)

Polymerization with metallocene catalysts. Hydrooligomerization and NMR investigations concerning the microstructure of poly(cyclopentenes)

How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study

Palladium-Catalyzed Cross-Coupling of Monochlorosilanes and Grignard Reagents

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