Synthesis, characterization, crystal structures, Hirshfeld surface analysis and theoretical calculations of some new bisphosphoramidate derivatives and novel binuclear triorganotin(IV) complexes with diphosphoryl ligand

Gholivand K., Azadbakht M., Maghsoud Y., Hosseini M., Kazak C.

JOURNAL OF ORGANOMETALLIC CHEMISTRY, cilt.879, ss.27-39, 2019 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 879
  • Basım Tarihi: 2019
  • Doi Numarası: 10.1016/j.jorganchem.2018.10.012
  • Dergi Adı: JOURNAL OF ORGANOMETALLIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Index Chemicus (IC)
  • Sayfa Sayıları: ss.27-39
  • Anahtar Kelimeler: Triorganotin(IV), Bisphosphoramidate, Crystal structure, Hirshfeld surfaces, Theoretical studies, NONLINEAR-OPTICAL PROPERTIES, ORGANOTIN COMPOUNDS, INTERMOLECULAR INTERACTIONS, DIORGANOTIN DIHALIDE, MOLECULAR-STRUCTURES, SCHIFF-BASES, BIOACTIVATION, ACTIVATION, DICHLORIDE, PRODRUGS
  • Ondokuz Mayıs Üniversitesi Adresli: Evet

Özet

A series of new bisphosphoramidate and (thio) phosphoramidate derivatives with the general formula R1R2P(X)-Y-P(X)R1R2 have been synthesized and characterized by IR and NMR spectroscopies (L-1-L-12). The crystal structure of compound 1,4-[(C2H5O)(2)P(S)(CH2)(3)NH](2)C4H8N2 (L-4) is also investigated by X-ray diffraction analysis. Two novel organotin(IV) complexes mu-{1,4-[(C6H5)(2)P(O)(CH2)(3)NH](2)C4H8N2}[SnR3Cl](2), R3SnCl (R = phenyl/butyl), C-1 and C-2, respectively, are prepared by the reaction of new diphosphoryl ligand L-1 and R3SnCl under different conditions. C-1 and C-2 are characterized by IR and NMR spectroscopies and X-ray crystallography diffraction analysis. X-ray analysis illustrates that both complexes have similar structures containing binuclear triorganotin(IV) skeletons and ligand coordinates in a bridging mode through two phosphoryl groups. Sn(IV) coordination geometries are distorted trigonal bipyramidal (TBP) for C-1, and C-2 structures contained binuclear arrangement with two SnPh3Cl/SnBu3Cl groups linked via the bridging diphosphoryl ligand. The organization of the crystal structures and the intermolecular interactions are discussed. Hirshfeld surfaces and two-dimensional fingerprint plots are used to study short intermolecular contacts in C-1, C-2, and L-4. Finally, the influence of chain length and the effects of various substituents on P=O and P=S bond strength in synthesized ligands (L-1-L-12) and optimized ligands (L-13-L-17) are theoretically investigated by NBO analysis to survey the character of mentioned bonds in these ligands. The AIM analysis is also used to determine the nature of the P=O bond in L-1 and also P=O and O center dot center dot center dot Sn4+ bonds in C-1 and C-2. Results show ionic character for O center dot center dot center dot Sn4+ interaction in both complexes and mostly electrostatic character for P=O bond in the free ligand, but with a little shift to the covalent character after the complexation. (C) 2018 Elsevier B.V. All rights reserved.