Enhancement of Ethylene and Ethylene/1-Hexene (Co)polymerization Activities by Titanium(IV) and Zirconium(IV) Complexes Bearing Constrained Hydroxyindanone-Imine Ligands.

A new series of catalysts for ethylene and ethylene/1-hexene (co)polymerizations bearing constrained hydroxyindanone-imine ligands was developed for titanium(IV) and zirconium(IV) metals with variations of steric and electronic contributions on the ligands. X-ray crystal structures revealed significantly higher open space for the constrained titanium and zirconium complexes, compared to the conventional FI counterparts. Upon activation with MAO, significantly higher ethylene polymerization activities (up to 379.4 kg-PE/mmol-M h for Zr) and notably almost doubled 1-hexene content in the ethylene/1-hexene copolymerizations were observed as a result of the constrained five-membered ring backbone.

Ring-Opening Co- and Terpolymerization of Epoxides, Cyclic Anhydrides, and l-Lactide Using Constrained Aluminum Inden Complexes.

Seven constrained aluminum inden complexes having different substituents and diamine backbones were developed for the ring-opening copolymerization (ROCOP) of epoxides and bulky cyclic anhydrides giving alternating polyesters with Tg ranging from 49 to 226 °C. Among several catalyst/cocatalyst screenings, the aluminum inden complex having a rigid phenylene backbone coupled with 4-dimethylaminopyridine showed the best performance giving linear polyesters. In the case of cyclohexene oxide (CHO) and succinic anhydride (SA), the linear poly(CHO-alt-SA) could be transformed to cyclic polymer when the polymerization was left under prolonged reaction time to induce intramolecular transesterification. The kinetic studies of the ROCOP revealed a zeroth-order dependence on cyclic anhydride and a first-order dependence on epoxide and the catalyst. The catalysts can be extended efficiently to the one-pot CHO/PA/l-lactide terpolymerization giving uncommon tapered copolymers of poly(CHO-alt-PA) and PLA via switchable polymerization.

Highly Active Homoleptic Zinc and Magnesium Complexes Supported by Constrained Reduced Schiff Base Ligands for the Ring-Opening Polymerization of Lactide.

New homoleptic zinc and magnesium complexes containing constrained reduced Schiff base ligands based on substituted 7-hydroxy-1-indanone were successfully synthesized and used as a catalyst for the polymerization of lactide. The ligands contain a side arm having different basicity because dimethylamino, pyridyl, and furfuryl groups are shown to greatly affect the polymerization rates. The homoleptic zinc complex containing constrained reduced Schiff base ligands and a dimethylamino side arm was highly active, giving a 92% conversion of l-lactide in 3 min using [LA]:[Zn]:[BnOH] = 500:1:2 at room temperature. The polymerization is pseudo-first-order dependent on the LA concentration. Well-controlled and living behavior of the zinc complex was observed and demonstrated in the preparation of stereodiblock and triblock copolymers of l-, d-, and rac-lactide in a one-pot sequential synthesis with a predictable block length, block sequence, and narrow dispersity rapidly in 10 min. Stereocomplex formation was observed for PLA made sequentially from 100 l-LA, 100 rac-LA, and 100 d-LA having a high Tm of up to 220 °C.

Polymerization of ε-Caprolactone Using Bis(phenoxy)-amine Aluminum Complex: Deactivation by Lactide.

Polymerizations of biodegradable lactide and lactones have been the subjects of intense research during the past decade. They can be polymerized/copolymerized effectively by several catalyst systems. With bis(phenolate)-amine aluminum complex, we have shown for the first time that lactide monomer can deactivate the aluminum complex during the ongoing polymerization of ε-caprolactone to a complete stop. After hours of dormant state, the aluminum complex can be reactivated again by heating at 100 °C without the addition of any external chemicals still giving polymer with narrow dispersity. Studies using NMR, in situ FTIR, and single-crystal X-ray crystallography indicated that the coordination of the carbonyl group in lactyl unit was responsible for the unusual behavior of lactide. In addition, the unusual methyl-migration from methyl lactate ligand to the amine side chain of the aluminum complex was observed through intermolecular nucleophilic-attack mechanism.

Epoxide/CO2 Cycloaddition Reaction Catalyzed by Indium Chloride Complexes Supported by Constrained Inden Schiff-Base Ligands.

Cyclic carbonates have received significant interests for uses as reagents, solvents, and monomers. The coupling reaction of epoxides with carbon dioxide (CO2 ) to produce cyclic carbonate is an attractive route which can significantly reduce greenhouse gas emissions and environmental hazards. Herein, a series of five indium chloride complexes supported by inden Schiff-base ligands were reported along with four X-ray crystal structures. The constrained five-membered rings were added to the ligands to enhance the coordination of epoxides to the In metal. From the catalyst screening, In inden complex having tert-butyl substituents and propylene backbone in combination with tetrabutylammonium bromide (TBAB) exhibited the highest catalytic activity (TON up to 1017) for propylene oxide/CO2 coupling reaction with >99 % selectivity for cyclic carbonate under solvent-free conditions. In addition, the catalyst was shown to be active at atmospheric pressure of CO2 at room temperature. The catalyst system can be applied to various internal and terminal epoxide substrates to exclusively produce the corresponding cyclic carbonates.

Complexity of imine and amine Schiff-base tin(II) complexes: drastic differences of amino and pyridyl side arms.

A series of homoleptic and heteroleptic imine and amine Schiff-base tin(II) complexes containing dimethylamino and pyridyl side arms were synthesized and structurally characterized. While the tin complexes containing the dimethylamino side arm could be prepared in good yield, unusual cyclodimerization and ligand dimerization were observed for the first time for Schiff-base tin complexes having a pyridyl side arm due to the added stabilization offered by the pyridyl ring. The amine Schiff-base tin(II) complexes were active for the ring-opening copolymerization of succinic anhydride (SA) and cyclohexene oxide (CHO) at 110 °C giving highly alternating poly(SA-alt-CHO).

Comparative bindings of lactones, lactide, and cyclic carbonates: experimental insights into the coordination step of polymerization.

Comparative bindings of several renowned monomers were investigated experimentally using B(C6F5)3 as a Lewis acid model for the coordination step in ring-opening polymerization. A complete series of the X-ray crystal structures of the B(C6F5)3 adducts with the monomers was reported. The X-ray structural studies and spectroscopic data revealed a coordination strength in the order lactones > tetrahydrofuran > cyclic carbonates > lactide.

Unmodified gold nanoparticles as a simple colorimetric probe for ramoplanin detection.

In this paper unmodified gold nanoparticles (AuNPs) were used as a sensing element to detect ramoplamin. Detection relies on the fact that the dispersed AuNPs solution is red due to the intense surface plasmon absorption band at 530 nm whereas the AuNPs solution in the presence of ramoplanin is blue. Upon aggregation, there is a significant change in absorbance intensity at 620 nm. Based on the aggregation of AuNPs induced by ramoplanin, a simple colorimetric method was developed for determining the of ramoplanin concentration. Experimental conditions influencing the analytical performance such as particle size, amount of AuNPs, incubation time and pH were evaluated. Under the optimized experimental conditions, this method could detect ramoplanin in a linear range from 0.30 to 1.30 ppm with a detection limit of 0.01 ppm and exhibited good reproducibility, selectivity and recovery. Analysis time of this assay was only 2 min. To investigate its potential applicability, this assay was successfully applied for the determination of ramoplanin in urine samples without costly instruments.

Reverse orders of reactivities in the polymerization of cyclic esters using N(2)O(2) aluminium alkoxide complexes.

Three aluminium alkoxide complexes containing N(2)O(2) bis(phenoxy)-amine ligands were synthesized from reactions of the corresponding N(2)O(2) ligands with Al(O(i)Pr)(3) in toluene. Different amine side chains of the ligands included pyridine (1), CH(2)NMe(2) (2), and CH(2)NEt(2) (3). The related chloro aluminium analog (4) was prepared from a reaction between AlCl(3) and the potassium salt of the N(2)O(2) ligand having CH(2)NMe(2) side chain. X-Ray crystallography reveals that complexes 3 and 4 have a monomeric five-coordinate aluminium center. Complexes 1-3 catalyzed the polymerization of epsilon-caprolactone (epsilon-CL) at 70 degrees C in toluene with the relative reactivities of 1<2< 3. In contrary, only complex 1 was active for the polymerization of lactide under the same polymerization conditions. (1)H NMR spectroscopy shows that treatment of 2 with 1 equivalent of lactide afforded the ring-opened product L(2)Al-OCH(Me)C(O)OCH(Me)C(O)O(i)Pr. Electronic effects are believed to be responsible for the observed trend in the epsilon-CL polymerization rates. On the other hand, steric hindrance at the amine side chain is the main contributor to the observed rates of lactide polymerization.