scholarly journals Pentamethylcyclopentadienyl Molybdenum(V) Complexes Derived from Iodoanilines: Synthesis, Structure, and ROP of ε-Caprolactone

Catalysts ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 1554
Author(s):  
Tian Xing ◽  
Mark R. J. Elsegood ◽  
Sophie H. Dale ◽  
Carl Redshaw
Keyword(s):  
Molecular Weight ◽  
Comparative Studies ◽  
Ring Opening ◽  
Kinetic Studies ◽  
Ring Opening Polymerization ◽  
Molecular Structures ◽  
Low Molecular Weight ◽  
End Groups ◽  
Amine Complex ◽  
Reaction Stoichiometry

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.

Diol glycidyl ether-bridged low molecular weight PEI as potential gene delivery vehicles

2015 ◽  
Vol 3 (13) ◽  
pp. 2660-2670 ◽  
Author(s):  
Qian Guo ◽  
Yan-Hong Liu ◽  
Miao-Miao Xun ◽  
Ji Zhang ◽  
Zheng Huang ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Gene Delivery ◽  
Ring Opening ◽  
Transfection Efficiency ◽  
Glycidyl Ether ◽  
Ring Opening Polymerization ◽  
Low Molecular Weight ◽  
Delivery Vehicles ◽  
Gene Delivery Vehicles

PEI 600-based polymers were synthesized via ring-opening polymerization and exhibited much better transfection efficiency and biocompatibility than PEI 25 kDa.

scholarly journals Chiral 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-Catalyzed Stereoselective Ring-Opening Polymerization of rac-Lactide: High Reactivity for Isotactic Enriched Polylactides (PLAs)

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2365 ◽  
Author(s):  
Qaiser Mahmood ◽  
Guangqiang Xu ◽  
Li Zhou ◽  
Xuanhua Guo ◽  
Qinggang Wang
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Kinetic Studies ◽  
Monomer Conversion ◽  
Ring Opening Polymerization ◽  
High Reactivity ◽  
Chiral Hplc ◽  
Nmr Spectrum ◽  
Molecular Weight Distributions ◽  
A Chain

Chiral 4,8-diphenyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (DiPh-TBD) was synthesized and applied to a ring-opening polymerization of rac-lactide (rac-LA). The chiral DiPh-TBD promoted the synthesis of isotactic enriched polylactides (PLAs) with controlled molecular weight and narrow molecular weight distributions under mild, metal-free conditions. When the [rac-LA]/[Cat.] ratio was 100/1, full monomer conversion was achieved within only 1 min and a moderate probability of 0.67 meso dyads (Pm) was obtained at room temperature. A chain-end control mechanism (CEC) was found to be responsible for the isoselectivity based on the homodecoupled 1H NMR spectrum, the chiral HPLC measurement, and kinetic studies.

scholarly journals Fast and Convenient Synthesis of Amine-Terminated Polylactide as a Macroinitiator forω-Benzyloxycarbonyl-L-Lysine-N-Carboxyanhydrides

2011 ◽  
Vol 2011 ◽  
pp. 1-7 ◽  
Author(s):  
Mingjie Ju ◽  
Feirong Gong ◽  
Shujun Cheng ◽  
Yun Gao
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Low Molecular Weight ◽  
Amine Group ◽  
H Nmr ◽  
Convenient Synthesis ◽  
Ft Ir ◽  
Chain Lengths

Amine-terminated poly (L-lactide) (NH2-PLLA) with various chain lengths were successfully synthesized by sequential tert-butyl-N-(3-hydroxypropyl) carbamate initiated bulk ring-opening polymerization (ROP) of L-lactide (L-LA) in the presence of Stannous(II) 2-ethylhexanoate (Sn(Oct)2) and deprotection of theN-tert-butoxycarbonyl (Boc) group at the end of the polymer chain. The polymers obtained were characterized by FT-IR,1H NMR, and GPC method. NH2-PLLA thus prepared was used to initiate the polymerization of ω-benzyloxycarbonyl-L-lysine-N-carboxyanhydride (Lys (Z)-NCA), and the result confirmed the high nucleophilicity of the terminal amine group. This method was not only suitable for the preparation of low molecular weight NH2-PLLA, but also quite efficient in the synthesis of high molecular weight samples.

Catalytic Ring-Opening Polymerization of Renewable Macrolactones to High Molecular Weight Polyethylene-like Polymers

2011 ◽  
Vol 44 (11) ◽  
pp. 4301-4305 ◽  
Author(s):  
Inge van der Meulen ◽  
Erik Gubbels ◽  
Saskia Huijser ◽  
Rafaël Sablong ◽  
Cor E. Koning ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Ring Opening ◽  
Ring Opening Polymerization

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

1995 ◽  
Vol 73 (11) ◽  
pp. 2069-2078 ◽  
Author(s):  
Timothy J. Peckham ◽  
Daniel A. Foucher ◽  
Alan J. Lough ◽  
Ian Manners
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Monoclinic Space Group ◽  
Organometallic Polymers ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cyclopentadienyl Ligands ◽  
Sterically Demanding ◽  
High Molecular Weight Poly

The silicon-bridged [1]ferrocenophane Fe(η-C5H3SiMe3)2(SiMe2) (5) was synthesized via the reaction of Li2[Fe(η-C5H3SiMe3)2]•tmeda (tmeda = tetramethylethylenediamine) with Me2SiCl2 in hexanes. The disilane-bridged [2]ferrocenophane Fe(η-C5H3SiMe3)2(Si2Me4) (7) was prepared using a similar route from the disilane ClMe2SiSiMe2Cl. Despite the presence of sterically demanding SiMe3 substituents on the cyclopentadienyl rings, compound 5 was found to undergo thermal ring-opening polymerization at 170 °C to produce very soluble, high molecular weight poly(ferrocenylsilane) 6 with Mw = 1.4 × 105, Mn = 8.4 × 104. However, the [2]ferrocenophane 7 was found to be resistant to thermal ring-opening polymerization even at 350 °C and decomposed above 380 °C. A single-crystal X-ray diffraction study of 7 revealed that the steric interactions between the bulky SiMe3 groups are relieved by a significant twisting of the disilane bridge with respect to the plane defined by the centroids of the cyclopentadienyl ligands and the metal atom. The angle between the planes of the cyclopentadienyl rings in 7 was found to be 5.4(6)°, slightly greater than that in the non-silylated analogue Fe(η-C5H4)2(Si2Me4) (4a) (4.19(2)°), and dramatically less than the corresponding tilt angle of the strained, polymerizable, silicon-bridged [1]ferrocenophane Fe(η-C5H4)2(SiMe2) (1) (20.8(5)°). The length of the Si—Si bond in 7 (2.342(3) Å) was found to be close to the sum of the covalent radii (2.34 Å). Crystals of 7 are monoclinic, space group C2/c, with a = 23.689(3) Å, b = 11.174(1) Å, c = 31.027(3) Å, β = 109.16(1)°, V = 7758(2) Å3, and Z = 12. Keywords: ring-opening polymerization, ferrocenophane, organometallic polymers.

Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer

2015 ◽  
Vol 6 (4) ◽  
pp. 514-518 ◽  
Author(s):  
Petra J. M. Bouten ◽  
Dietmar Hertsen ◽  
Maarten Vergaelen ◽  
Bryn D. Monnery ◽  
Marcel A. Boerman ◽  
...  
Keyword(s):  
Methyl Ester ◽  
Ring Opening ◽  
Kinetic Studies ◽  
Ring Opening Polymerization ◽  
Cationic Ring Opening Polymerization

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

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