Search results for "olefin"

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu2X2)n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, …

2016

CuI reacts with E-PhS(CH2CH═CHCH2)SPh, L1, to afford the coordination polymer (CP) [Cu2I2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1a). The unprecedented square-grid network of 1 is built upon alternating two-dimensional (2D) layers with an ABAB sequence and contains rhomboid Cu2(μ2-I)2 clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging L1 ligands, contains exclusively dinuclear units with short Cu···Cu separations [2.6485(7) A; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) A. The same network is observed when CuBr reacts with L1. In the 2D network of [Cu2Br2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1b), isotype to 1a, one square-grid-type layer contain…

Organolanthanides, catalysts for specific olefin-diene copolymerization: access to new materials

2001

Abstract Non-hindered ansa dicyclopentadienylallyl complexes of samarium, [(CMe2C5H4)2Sm(allyl)]n, and (CMe2C5H4)2Sm(allyl)L (L=THF or allylLi) polymerize isoprene without an aluminum cocatalyst. The polymerizations are highly stereospecific, affording nearly quantitatively 1–4 trans polyisoprene. In the presence of linear 1-olefins, copolymers are formed, with 6–10% of olefin inserted; the 1–4 trans structure of the polyisoprene chain is not altered, and only one olefin molecule is inserted between two polyisoprene fragments. In the common initiator of these three catalytic systems, the (CMe2C5H4)2Sm(allyl) moiety, only one vacant site would be available. As a consequence of the presence o…

Revisiting the photochemical synthesis of [FeFe]-hydrogenase mimics: reaction optimization, mechanistic study and electrochemical behaviour

2020

The photoreaction of [(μ-S)2Fe2(CO)6] and alkenes or alkynes has been optimized to readily obtain functionalized [FeFe]-hydrogenase mimics. Irradiation under low CO pressure in THF produces the corresponding photo-adducts in good/acceptable (alkenes/alkynes) yields, with retention of the starting olefin stereochemistry. DFT-calculations provide plausible reaction pathways in both, singlet and triplet states. The DFT-calculation based in the singlet state is energetically more favorable. The electrochemical behavior of the synthesized compounds is also presented, including studies in acidic media. The electrochemical properties of the products vary in the presence of a double bond (cycloaddi…

Enantioselective epoxidation of olefins with molecular oxygen catalyzed by gold(III): A dual pathway for oxygen transfer

2009

Abstract A chiral gold(III) complex has been prepared that performs the epoxidation of olefins in the presence of O 2 , PhIO, or bleach. Catalytic experiments with 18 O show that O 2 is activated on the catalyst and can be directly incorporated into the epoxide through a non-radical mechanism that probably involves formation of gold, oxo, or peroxo species. In addition to this, there is a parallel radical mechanism operating that yields α , β -unsaturated ketones and alcohols as subproducts. Electrochemical and UV–Vis experiments confirmed the occurrence of a Au(III)/Au(I) redox cycle during the catalytic epoxidation in a mechanism sustained by molecular oxygen.

Diene/olefin/polar monomer copolymerisation: unprecedented functional polymers from a rare earth catalyst

2002

An ansasamarocene allyl system is an efficient initiator which polymerises 1,3-dienes, copolymerises dienes and long-chain α-olefins or α,ω-dienes to give functionalisable polymers. It also polymerises caprolactone and allows the controlled diblock copolymerisation of isoprene or isoprene/ α-olefin copolymer and caprolactone.

Olefin Polymerisation Catalysts

2002

Polyolefins, which are products of polymerisation of unsaturated hydrocarbons of the olefin series, have a molecular weight in the range from several thousands to several millions. Depending on the type of monomer and method and mechanism of polymerisation the resulting polyolefins may differ in their structure and molecular weight. They can be used in many applications, for example as constructional plastics and in packaging, fibres, rubbers, and also as additives to control the viscosity of motor oils(1). As regards their scale of production polyolefins occupy the top position among mass-produced polymers(2).

New Viscoelastic Materials Obtained by Insertion of anα-Olefin in atrans-Polyisoprene Chain with a Single-Component Organolanthanide Catalyst

2001

Copolymerisation of isoprene with C 6 -C 18 a-olefins by a single component organolanthanide catalyst affords poly(trans-1,4-isoprene) containing 6-10% of inserted olefin. The mechanical properties of highly crystalline transpolyisoprene are dratically modified after insertion of the alkyl chains, leading to quasi-amorphous viscoelastic materials.

Chemodiscrimination of Olefin Bonds Through Cross‐Metathesis Reactions – Synthesis of Functionalized β‐Lactam and β‐Amino Acid Derivatives

2019

Diastereoselective synthesis of fluorinated, seven-membered beta-amino acid derivatives via ring-closing metathesis.

2003

[reaction: see text] Cis and trans seven-membered gamma,gamma-difluorinated beta-amino acid derivatives (III) have been prepared with a sequence that starts with imidoyl halides (I), which are condensed with suitable ester enolates to give intermediates (II). These, in turn, can be cyclized by means of a ring-closing olefin metathesis reaction and the product stereoselectively reduced to yield compounds (III) in good overall yields.

Novel polyolefin materials via catalysis and reactive processing

1998

Recent advances in transition metal catalyzed olefin polymerization and melt processing stimulate the production of new polymers derived from old monomers Modern polyolefin processes do not require polymer purification and give excellent control of molecular and supermolecular polyolefin architectures. Progress in catalyst design and preparation of tailor-made homo-and copolymers is highlighted for isotactic, syndiotactic, atactic and stereoblock polypropylene (PP), novel 1-olefin copolymers, and ethylene copolymers with polar monomers, e.g., CO and acrylics Today polyethylene short-and long-chain-branching is controlled either by uniform ethylene copolymerization with 1-olefins using singl…