%0 Journal Article %A Javad Sabounchei, Seyyed %A Sayadi, Mohsen %A Bayat, Mehdi %A Sedghi, Asiyeh %A Gable, Robert W. %D 2017 %T Synthesis, X-ray structural and DFT studies of n-membered ring P, C-chelated complexes of Pd(II) and Pt(II) derived from unsymmetrical phosphorus ylides and application of Pd(II) complexes as catalyst in Suzuki reaction %U https://tandf.figshare.com/articles/journal_contribution/Synthesis_X-ray_structural_and_DFT_studies_of_i_n_i_-membered_ring_P_C-chelated_complexes_of_Pd_II_and_Pt_II_derived_from_unsymmetrical_phosphorus_ylides_and_application_of_Pd_II_complexes_as_catalyst_in_Suzuki_reaction/5544544 %R 10.6084/m9.figshare.5544544 %2 https://tandf.figshare.com/ndownloader/files/9603823 %K Palladium and platinum %K ylide %K X-ray structure %K Suzuki reaction %K DFT, EDA analysis %K EDA-NOCV, nature of bond %X

The phosphonium salts [Ph2P(CH2)nPPh2CH2C(O)C6H4-m-OMe]Br (n = 1 (S1) and n = 2 (S2)) were synthesized in the reaction of bis(diphenylphosphino)methane (dppm) and bis(diphenylphosphino)ethane (dppe) with 2-bromo-3ʹ-methoxy acetophenone, respectively. Further treatment with NEt3 gave the phosphorus ylides Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe (n = 1 (Y1) and n = 2 (Y2)). These ligands were treated with [MCl2(cod)] (M = Pd or Pt; cod = 1,5-cyclooctadiene) to give the P, C-chelated complexes, [MCl2(Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe)] (n = 1, M = Pd (3), Pt (4), and n = 2, M = Pd (5), Pt (6)). These compounds were characterized by elemental analysis, spectroscopic methods, UV–visible, and fluorescence emission spectra. Further, the structures of complexes 3 and 6 were characterized crystallographically. The palladium complexes 3 and 5 proved to be excellent catalysts for the Suzuki reactions of various aryl chlorides. Also, a theoretical study on the structure of complexes 3–6 has been investigated at the BP86/def2-SVP level of theory. The strength and nature of donor−acceptor bonds between the phosphorus ylides (L) and MCl2 fragment in the [LMCl2] (M = Pd, Pt, L = Y1, Y2) were studied by NBO and energy decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV).

%I Taylor & Francis