58046-12-1Relevant articles and documents
Versatile PNPO ligands for palladium and nickel catalyzed ethylene polymerization and copolymerization with polar monomers
Chen, Min,Liao, Daohong,Pang, Wenmin,Tan, Chen,Zou, Chen
, p. 281 - 289 (2020/12/28)
Asymmetric PO-type ligands are versatile platforms for palladium and nickel catalyzed ethylene polymerization as well as copolymerization of ethylene with polar monomers. In this work, a series of phosphinoamine phosphoramidate/phosphoramide ligands and the corresponding palladium/nickel catalysts were prepared, characterized and investigated in ethylene polymerization as well as copolymerization of ethylene with various polar monomers. The palladium and nickel complexes exhibited high activities in ethylene (co) polymerization, generating high-molecular-weight polyethylenes and copolymers of ethylene and polar monomers. The introduction of electron-donating substituents in the palladium catalytic system can significantly increase polymer molecular weights while maintaining high ethylene (co)polymerization activities. The less electronic donating substituents in the nickel catalysts led to increased catalytic activities in both ethylene polymerization and copolymerization with polar monomers. These results demonstrate the importance of ligand electronic effect in tuning the properties of nickel and palladium catalysts in ethylene polymerization and copolymerization reactions.
Kinetics and mechanism of the anilinolysis of dibutyl chlorophosphate in acetonitrile
Hoque, Md. Ehtesham Ul,Lee, Hai Whang
scheme or table, p. 663 - 669 (2012/05/19)
The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 °C. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.86-0.97) with the strongly basic anilines while primary normal (kH/kD = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine (R1O)(R2O)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the kH/kD values with X.
Anilinolysis of dimethyl isothiocyanophosphate in acetonitrile
Barai, Hasi Rani,Adhikary, Keshab Kumar,Lee, Hai Whang
, p. 2769 - 2772 (2012/11/07)
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