کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1404807 1501698 2016 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Synthesis, spectral, structural and computational studies on NiS4 and NiS2NP chromophores: Anagostic and C–H⋯π (chelate) interactions in [Ni(dtc)(PPh3)(NCS)] (dtc = N-(2-phenylethyl)-N-(4-methoxybenzyl)- dithiocarbamate and N-(2-phenylethyl)-N-(4-chlorobe
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آلی
پیش نمایش صفحه اول مقاله
Synthesis, spectral, structural and computational studies on NiS4 and NiS2NP chromophores: Anagostic and C–H⋯π (chelate) interactions in [Ni(dtc)(PPh3)(NCS)] (dtc = N-(2-phenylethyl)-N-(4-methoxybenzyl)- dithiocarbamate and N-(2-phenylethyl)-N-(4-chlorobe
چکیده انگلیسی


• Twelve new Ni(II)-functionalized dithiocarbamate complexes were synthesized.
• X-ray crystal structural analysis revealed the trans effect of PPh3 on Ni–S bonds.
• Anagostic (C–H⋯Ni) and C–H⋯π(chelate) interactions are observed.
• Trans effect of triphenylphosphine is absent in gaseous state.

Bis(N-(2-phenylethyl)-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1–6) and (N-(2-phenylethyl)-N-substituted benzyldithiocarbamato-S,S′)(thiocyanato-N) (triphenylphosphine)nickel(II) (7–12) [substituted benzyl = 2HO–C6H4–CH2– (1,7), 3HO–C6H4–CH2– (2,8), 4HO–C6H4–CH2– (3,9), 4CH3O–C6H4–CH2– (4,10), 4F–C6H4–CH2– (5,11), 4Cl–C6H4–CH2– (6,12)] complexes have been synthesized and characterized by elemental analysis, IR, UV–Vis and NMR (1H and 13C) spectroscopy. In the case of heteroleptic complexes 7–12, the shift in vC-N values to higher wavenumber and the NCS2 carbon signals are shifted to downfield compared to the homoleptic complexes indicating the increasing strength of thioureide vC-N bond due to the presence of π-accepting triphenylphosphine ligand in heteroleptic complexes. Electronic spectral studies on all the complexes (1–12) suggest square planar geometry around the nickel(II). Structures of 10 and 12 have been elucidated by X-ray crystallography. The dithiocarbamate anions in 10 and 12 chelate to the nickel atom. Both the structures reveal C–H⋯Ni intramolecular anagostic interaction. C–H⋯π (chelate) is observed in complexes 10. Supramolecular frame works are stabilised by C–H⋯S, C–H⋯π and C–H⋯Cl non-covalent interaction. The molecular geometry, HOMO-LUMO in the ground state and MEP have been calculated for 10 and 12 using Hartree-Fock (HF) method with LANL2DZ basic set. Molecular electrostatic potential diagram of complexes 10 and 12 support the partial double bond character of C–N (thioureide) bond in dithiocarbamate ligands.

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ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure - Volume 1119, 5 September 2016, Pages 385–395
نویسندگان
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