Bis(pyrazolylmethyl)pyridine Zn(II) and Cu(II) complexes: Molecular structures and kinetic studies of ring-opening polymerization of ε-caprolactone

2016 ◽  
Vol 413 ◽  
pp. 24-31 ◽  
Author(s):  
Mnqobi Zikode ◽  
Stephen O. Ojwach ◽  
Matthew P. Akerman
Catalysts ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 1554
Author(s):  
Tian Xing ◽  
Mark R. J. Elsegood ◽  
Sophie H. Dale ◽  
Carl Redshaw

The reaction of [Mo(η-C5Me5)Cl4] with the ortho-, meta-, or para-iodo-functionalized anilines 2-IC6H4NH2, 3-IC6H4NH2, 4-IC6H4NH2 yields imido or amine products of the type [Mo(η-C5Me5)Cl2(IC6H4N)] (2-I, 1, 3-I, 3, 4-I, 5) or [Mo(η-C5Me5)Cl4(IC6H4NH2)] (3-I, 2, 4-I, 4), respectively, depending on the reaction stoichiometry/conditions; we were unable to isolate an amine complex of the 2-I derivative. The reaction of [Mo(η-C5Me5)Cl4] with one equivalent of 2-I,4-FC6H3NH2 in the presence of Et3N afforded [Mo(η-C5Me5)Cl2(2-I,4-FC6H3N)]·MeCN (6·MeCN), which, upon exposure to air, afforded the Mo(VI) imido complex [Mo(η-C5Me5)Cl3(2-I,4-FC6H3N)] (7). For comparative studies, the structure of the aniline (C6H5NH2)-derived complex [Mo(η-C5Me5)Cl2(2-C6H3N)] (8) has also been prepared. The molecular structures of 1–8 have been determined and reveal packing in the form of zig-zag chains or ladders. The complexes catalyze, in the presence of benzyl alcohol under N2, the ring-opening polymerization (ROP) of ε-caprolactone affording relatively low molecular weight products. The MALDI-ToF spectra indicate that a number of polymer series bearing a variety of end groups are formed. Conducting the ROPs as melts or under air results in the isolation of higher molecular weight products, again bearing a variety of end groups. Kinetic studies reveal the aniline-derived imido complex 8 performs best, whilst a meta-iodo substituent and a Mo(V) centre are also found to be beneficial. The structures of the side products 2-IC6H4NH3Cl and 3-IC6H4NH3Cl are also reported.


2015 ◽  
Vol 6 (4) ◽  
pp. 514-518 ◽  
Author(s):  
Petra J. M. Bouten ◽  
Dietmar Hertsen ◽  
Maarten Vergaelen ◽  
Bryn D. Monnery ◽  
Marcel A. Boerman ◽  
...  

Kinetic studies on the homo- and copolymerization of 2-methoxycarboxyethyl-2-oxazoline with 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline is discussed.


2001 ◽  
Vol 20 (20) ◽  
pp. 4207-4210 ◽  
Author(s):  
Denise Barbier-Baudry ◽  
Sebastian Heiner ◽  
Marek M. Kubicki ◽  
Estelle Vigier ◽  
Marc Visseaux ◽  
...  

Polyhedron ◽  
2016 ◽  
Vol 110 ◽  
pp. 63-72 ◽  
Author(s):  
Ekemini D. Akpan ◽  
Stephen O. Ojwach ◽  
Bernard Omondi ◽  
Vincent O. Nyamori

2021 ◽  
Vol 47 (2) ◽  
pp. 144-154
Author(s):  
G. G. Skvortsov ◽  
A. V. Cherkasov ◽  
D. L. Vorozhtsov ◽  
E. S. Shchegravina ◽  
A. A. Trifonov

Abstract The reaction of lithium β-diketiminate [{2,6-Me2C6H3N=CMe}2CH]Li with benzophenone in toluene at 25°C affords the coordination complex [{2,6-Me2C6H3N=CMe}2CH]Li(Ph2C=O) (I). New keto-β-diketimine {2,6-Me2C6H3N=C(Me)}2CHC(tert-Bu)=O (II) is synthesized by the reaction of tert-Bu(C=O)Cl with [{2,6-Me2C6H3N=CMe}2CH]Li. The metallation of keto-β-diketimine II with n-butyllithium in THF at 0°C gives lithium keto-β-diketiminate {[{2,6-Me2C6H3N=C(Me)}2CС(tert-Bu)=O]Li(THF)}n (III). The exchange reaction of YCl3 with compound III (molar ratio 1 : 2, THF) affords the yttrium bis(keto-diketiminate) complex [{2,6-Me2C6H3N=C(Me)}2CС(tert-Bu)=O]2Y(μ2-Cl)2L-(THF)2 (IV). The molecular structures of complexes I, III, and IV are determined by X-ray diffraction analysis (CIF files CCDC nos. 2001131 (I), 2001132 (III), and 2001133 (IV)). Complex IV in the crystalline state exists as an ate complex with one LiCl molecule. Complexes I, III, and IV are catalysts of ring-opening polymerization of ε-caprolactone in toluene at 25°С.


Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 210 ◽  
Author(s):  
Orlando Santoro ◽  
Carl Redshaw

In this review, we discuss the use of titanium complexes bearing either bridged diphenolate or calix[n]arene (n = 4, 6, 8) ligation, in the formation of plastics from α-olefins or via the ring opening polymerization (ROP) of cyclic esters. The syntheses, molecular structures and catalytic behaviour of these systems are discussed, as well as where possible, the properties of the resultant polymers.


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