The Experts below are selected from a list of 228 Experts worldwide ranked by ideXlab platform
Sadahito Aoshima - One of the best experts on this subject based on the ideXlab platform.
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Design of Benign Initiator for Living Cationic Polymerization of Vinyl Ethers: Facile in Situ Generation of Vinyl Ether–Hydrogen Halide Adducts and Subsequent Controlled Polymerization without a Lewis Acid Catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
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design of benign initiator for living cationic polymerization of vinyl ethers facile in situ generation of vinyl ether Hydrogen Halide adducts and subsequent controlled polymerization without a lewis acid catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
Arihiro Kanazawa - One of the best experts on this subject based on the ideXlab platform.
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Design of Benign Initiator for Living Cationic Polymerization of Vinyl Ethers: Facile in Situ Generation of Vinyl Ether–Hydrogen Halide Adducts and Subsequent Controlled Polymerization without a Lewis Acid Catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
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design of benign initiator for living cationic polymerization of vinyl ethers facile in situ generation of vinyl ether Hydrogen Halide adducts and subsequent controlled polymerization without a lewis acid catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
Ryo Hashizume - One of the best experts on this subject based on the ideXlab platform.
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Design of Benign Initiator for Living Cationic Polymerization of Vinyl Ethers: Facile in Situ Generation of Vinyl Ether–Hydrogen Halide Adducts and Subsequent Controlled Polymerization without a Lewis Acid Catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
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design of benign initiator for living cationic polymerization of vinyl ethers facile in situ generation of vinyl ether Hydrogen Halide adducts and subsequent controlled polymerization without a lewis acid catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
Shokyoku Kanaoka - One of the best experts on this subject based on the ideXlab platform.
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Design of Benign Initiator for Living Cationic Polymerization of Vinyl Ethers: Facile in Situ Generation of Vinyl Ether–Hydrogen Halide Adducts and Subsequent Controlled Polymerization without a Lewis Acid Catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
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design of benign initiator for living cationic polymerization of vinyl ethers facile in situ generation of vinyl ether Hydrogen Halide adducts and subsequent controlled polymerization without a lewis acid catalyst
Macromolecules, 2014Co-Authors: Arihiro Kanazawa, Ryo Hashizume, Shokyoku Kanaoka, Sadahito AoshimaAbstract:A Lewis acid-free initiating system for cationic polymerization of alkyl vinyl ethers (VEs) was developed using CF3SO3H and tetraalkylammonium Halides (nBu4NX; X = I, Br, or Cl). The reaction of CF3SO3H, nBu4NX, and an alkyl VE generated a VE–Hydrogen Halide adduct. The labile carbon–halogen bond, such as a carbon–iodine bond, cleaved without a Lewis acid catalyst to induce the living cationic polymerization of VEs. Combining Halide anions with suitable nucleophilicities according to monomer reactivity was indispensable for controlled polymerization. Another prerequisite was that the polymerization be conducted at a suitable temperature. After the initiation step, the polymerization probably proceeded via the mechanisms similar to those for the previously reported systems using Hydrogen Halide and an ammonium salt with a noncoordinating anion. The present system was also useful as a facile method for the synthesis of VE–Hydrogen Halide adducts without the use of harmful gaseous Hydrogen Halides. The adduc...
Henry F. Schaefer - One of the best experts on this subject based on the ideXlab platform.
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Intermolecular interactions and proton transfer in the Hydrogen Halide–superoxide anion complexes
Physical chemistry chemical physics : PCCP, 2016Co-Authors: Sebastian J. R. Lee, J. Wayne Mullinax, Henry F. SchaeferAbstract:The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the Hydrogen Halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 A) Hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier Hydrogen Halides with the resulting complexes characterized as long (>1.89 A) Hydrogen bonds between Halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier Hydrogen Halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI.
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intermolecular interactions and proton transfer in the Hydrogen Halide superoxide anion complexes
Physical Chemistry Chemical Physics, 2016Co-Authors: Sebastian J. R. Lee, Wayne J Mullinax, Henry F. SchaeferAbstract:The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the Hydrogen Halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 A) Hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier Hydrogen Halides with the resulting complexes characterized as long (>1.89 A) Hydrogen bonds between Halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier Hydrogen Halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI.
