Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands.

ABSTRACT: This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a < 2b < 2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a > 2b > 2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.

SUBMITTER: Goonesinghe C

PROVIDER: S-EPMC8159295 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Reversible redox controlled acids for cationic ring-opening polymerization.

Project description:Advancements in externally controlled polymerization methodologies have enabled the synthesis of novel polymeric structures and architectures, and they have been pivotal to the development of new photocontrolled lithographic and 3D printing technologies. In particular, the development of externally controlled ring-opening polymerization (ROP) methodologies is of great interest, as these methods provide access to novel biocompatible and biodegradable block polymer structures. Although ROPs mediated by photoacid generators have made significant contributions to the fields of lithography and microelectronics development, these methodologies rely upon catalysts with poor stability and thus poor temporal control. Herein, we report a class of ferrocene-derived acid catalysts whose acidity can be altered through reversible oxidation and reduction of the ferrocenyl moiety to chemically and electrochemically control the ROP of cyclic esters.

| S-EPMC8356742 | biostudies-literature

Enhanced Reactivity of Aluminum Complexes Containing P-Bridged Biphenolate Ligands in Ring-Opening Polymerization Catalysis.

Project description:Aluminum complexes containing [RP(O)(2-O-3,5-tBu2C6H2)2]2- [R = tBu (3a), Ph (3b)] have been synthesized, structurally characterized, and their reactivity studied in comparison with those of their [RP(2-O-3,5-tBu2C6H2)2]2- [R = tBu (2a), Ph (2b)] analogs. Treating AlMe3 with one equiv of H2[3a-b] in THF at 0°C affords quantitatively [3a-b]AlMe, subsequent reactions of which with benzyl alcohol in THF at 25°C generate {[3a-b]Al(?2-OCH2Ph)}2. The methyl [3a-b]AlMe and the benzyloxide {[3a-b]Al(?2-OCH2Ph)}2 are all active for catalytic ring-opening polymerization (ROP) of ?-caprolactone and rac-lactide (rac-LA). Controlled experiments reveal that {[3a]Al(?2-OCH2Ph)}2 is competent in living polymerization. Kinetic studies indicate that [3a]AlMe, in the presence of benzyl alcohol, catalyzes ROP of rac-LA at a rate faster than [3b]AlMe and [2a]AlMe(THF) by a factor of 1.8 and 23.6, respectively, highlighting the profound reactivity enhancement in ROP catalysis by varying the P-substituents of these biphenolate complexes of aluminum.

| S-EPMC6300491 | biostudies-literature

Cis-selective ring-opening metathesis polymerization with ruthenium catalysts.

Project description:Cis-selective ring-opening metathesis polymerization of several monocyclic alkenes as well as norbornene and oxanorbornene-type monomers using a C-H activated, ruthenium-based metathesis catalyst is reported. The cis content of the isolated polymers depended heavily on the monomer structure and temperature. A cis content as high as 96% could be obtained by lowering the temperature of the polymerization.

| S-EPMC3278323 | biostudies-literature

Lignin-Based Polyols with Controlled Microstructure by Cationic Ring Opening Polymerization.

Project description:Lignin-based polyols (LBPs) with controlled microstructure were obtained by cationic ring opening polymerization (CROP) of oxiranes in an organosolv lignin (OL) tetrahydrofuran (THF) solution. The control on the microstructure and consequently on the properties of the LBPs such as hydroxyl number, average molecular weight, melting, crystallization and decomposition temperatures, are crucial to determine the performance and application of the derived-products. The influence of key parameters, for example, molar ratio between the oxirane and the hydroxyl groups content in OLO, initial OL concentration in THF, temperature, specific flow rate and oxirane nature has been investigated. LBPs with hydroxyl numbers from 35 to 217 mg KOH/g, apparent average Mw between 5517 and 52,900 g/mol and melting temperatures from -8.4 to 18.4 °C were obtained. The CROP procedure allows obtaining of tailor-made LBPs for specific applications in a very simple way, opening the way to introduce LBPs as a solid alternative to substitute currently used fossil-based polyols.

| S-EPMC7926755 | biostudies-literature

Cellulose-Derived Functional Polyacetal by Cationic Ring-Opening Polymerization of Levoglucosenyl Methyl Ether.

Project description:The unsaturated bicyclic acetal levoglucosenyl methyl ether was readily obtained from sustainable feedstock (cellulose) and polymerized by cationic ring-opening polymerization to produce a semicrystalline thermoplastic unsaturated polyacetal with relatively high apparent molar mass (up to ca. 36 kg mol-1 ) and decent dispersity (ca. 1.4). The double bonds along the chain can undergo hydrogenation and thiol-ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

| S-EPMC6916336 | biostudies-literature

Controlled Ring-Opening Metathesis Polymerization with Polyisobutylene-Bound Pyridine-Ligated Ru(II) Catalysts.

Project description:This study describes the use of polyisobutylene (PIB) to phase-anchor pyridine ligands that form a phase-separable Grubbs third-generation catalyst. We further show that this complex is useful in ring-opening metathesis polymerization (ROMP) reactions. These PIB-bound pyridine-ligated Grubbs catalysts provide the same benefits of control over polymer chain growth and polydispersity of the product as their low-molecular-weight analogs and reduce Ru leaching in ROMP products from approximately 16% (820 ppm residues) as seen with a similar pyridine-ligated catalyst to a value of approximately 3% (160 ppm residues). These labile ligands are shown to be as effective at generating separable metal complexes as less labile PIB-functionalized N-heterocyclic carbene catalyst ligands that are typically used for immobilization but that require a multistep synthesis.

| S-EPMC6640752 | biostudies-literature

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by MonoAryloxidePyrrolide (MAP) Catalysts.

Project description:We report the Z-selective and syndioselective polymerization of 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hepta-2,5-diene (NBDF6) and 3-methyl-3-phenylcyclopropene (MPCP) by monoaryloxide monopyrrolide imido alkylidene (MAP) catalysts of Mo. The mechanism of polymerization with syn-Mo(NAd)(CHCMe(2)Ph)(Pyr)(OHIPT) (1; Ad = 1-adamantyl, OHIPT = O-2,6-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(3)) as the initiator is proposed to consist of addition of monomer to the syn initiator to yield a syn first insertion product and propagation via syn insertion products. In contrast, the mechanism of polymerization with syn-Mo(NAr)(CHCMe(2)Ph)(Pyr)(OTPP) (4; Ar = 2,6-i-Pr(2)C(6)H(3), OTPP = 2,3,5,6-Ph(4)C(6)H) as the initiator at -78 °C consists of addition of monomer to the syn initiator to yield an anti first insertion product and propagation via anti insertion products. Polymerizations of NBDF6 and MPCP at room temperature initiated by 4 led to polymers without a regular structure. We propose that the syndiotacticity of cis polymers is the consequence of the required inversion at the metal center with each insertion of monomer, i.e., stereogenic metal control of the polymer structure. We also propose that the two mechanisms for forming cis,syndiotactic polymers arise as a consequence of the relative steric bulk of the imido and phenoxide ligands.

| S-EPMC3074984 | biostudies-literature

Copper(II) complexes with imino phenoxide ligands: synthesis, characterization, and their application as catalysts for the ring-opening polymerization of rac-lactide.

Project description:Four new copper complexes based on bidentate imino phenoxide ligands were synthesized and characterized by IR, UV-Vis spectroscopy, ESI mass spectrometry, single crystal X-ray diffraction, and electrochemistry. The crystal structures revealed that the copper(II) atoms are surrounded by phenolate oxygen and imine nitrogen atoms of two ligands in a distorted square-planar geometry. The existence of ligand-centered, as well as Cu(II)-centered quasi-reversible and reversible redox reactions are observed in the cyclic voltammetry experiments of all the complexes. All complexes are able to catalyze the ring-opening polymerization of rac-lactide yielding polymers with moderate molecular weights and moderately broad molecular weight distributions.

| S-EPMC5063905 | biostudies-other

Palladium complexes containing imino phenoxide ligands: synthesis, luminescence, and their use as catalysts for the ring-opening polymerization of <i>rac</i>-lactide.

Project description:AbstractThe preparation, structural characterization, luminescence, and catalytic activity of three palladium(II) complexes bearing imino phenoxide ligands are reported. The X-ray studies revealed that the complexes are mononuclear with palladium centres coordinated in a square-planar coordination environment. Two of the complexes are emissive in solution at room temperature. The catalytic activities towards the ring-opening polymerization of rac-lactide (rac-LA) were tested. Polymers with moderate molecular weights and relatively broad dispersity (Ð) were obtained. Kinetic studies revealed that the polymerization followed first-order kinetics.Graphical abstract

| S-EPMC5906497 | biostudies-literature

Highly active ruthenium metathesis catalysts enabling ring-opening metathesis polymerization of cyclopentadiene at low temperatures.

Project description:Development of versatile ruthenium olefin-metathesis catalysts with high activity, stability, and selectivity is a continuous challenge. Here we report highly controllable ruthenium catalysts using readily accessible and versatile N-vinylsulfonamides as carbene precursors. Catalyst initiation rates were controlled in a straightforward manner, from latent to fast initiating, through the facile modulation of the N-vinylsulfonamide ligands. Trifluoromethanesulfonamide-based catalysts initiated ultrarapidly even at temperatures as low as -60?°C and continuously propagated rapidly, enabling the enthalpically and entropically less-favored ring-opening metathesis polymerizations of low-strained functionalized cyclopentene derivatives, some of which are not accessible with previous olefin-metathesis catalysts. To our surprise, the developed catalysts facilitated the polymerization of cyclopentadiene (CPD), a feedstock that is easily and commonly obtainable through the steam cracking of naphtha, which has, to the best of our knowledge, not been previously achieved due to its low ring strain and facile dimerization even at low temperatures (below 0?°C).

| S-EPMC6712042 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data