Structural and Electronic Characterization of M(dppp)Cl2 Catalysts with M=Ni, Pd, and Pt: A DFT Study
عنوان مقاله: Structural and Electronic Characterization of M(dppp)Cl2 Catalysts with M=Ni, Pd, and Pt: A DFT Study
شناسه ملی مقاله: ISPST11_681
منتشر شده در یازدهمین سمینار بین المللی علوم و تکنولوژی پلیمر در سال 1393
شناسه ملی مقاله: ISPST11_681
منتشر شده در یازدهمین سمینار بین المللی علوم و تکنولوژی پلیمر در سال 1393
مشخصات نویسندگان مقاله:
Naeimeh Bahri-Laleh - Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran.
Mehdi Ghambarian - Gas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute, P.O. Box 14965-115, Tehran, Iran.
خلاصه مقاله:
Naeimeh Bahri-Laleh - Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran.
Mehdi Ghambarian - Gas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute, P.O. Box 14965-115, Tehran, Iran.
Experimental results indicate that the metal of the catalyst strongly affects the kinetics of polymerization and the regioregularity of synthesized poly-3-alkylthiophenes in M(dppp)Cl2 [dppp: 1,3-bis(diphenylphosphino) propane] catalyzed polymerization of 2,5-dibromo-3-alkylthiophene monomers. To make possible analyzing such effects in more detail, we have computationally investigated electronic structure of mostly known dppp including catalysts, M(dppp)Cl2, with M=Ni, Pd and Pt. To this end, molecular structure, partial charge of atoms, HOMO-LUMO energy gaps (ΔEHOMO-LUMO), and the values of the ρb, λ1, λ2, λ3 and 2ρb were fully determined by DFT and AIM analysis. Results from molecular structure analysis showed that, by replacing Ni atom with Pd and Pt, M-Cl and M-P bond length increase considerably, while Cl-M-Cl angle decrease slightly. Furthermore, ΔEHOMO-LUMO and partial charge on metal were decreased by this order Ni
کلمات کلیدی: Grignard metathesis polymerization, Coupling reactions, dppp, DFT, NBO, QTAIM
صفحه اختصاصی مقاله و دریافت فایل کامل: https://civilica.com/doc/579244/