کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1309408 975208 2009 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Low-spin, mononuclear, Fe(III) complexes with P,N donor hemilabile ligands: A combined experimental and theoretical study
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Low-spin, mononuclear, Fe(III) complexes with P,N donor hemilabile ligands: A combined experimental and theoretical study
چکیده انگلیسی

Two new mononuclear Fe(III) complexes, [FeCl3{PPh2(p-C6H4NMe2)-P}3](1) (PPh2(p-C6H4NMe2): 4-(dimethylamino)phenyldiphenylphosphine) and [FeCl3(PPh2py-P)(PPh2py-P,N)] (2) (PPh2py: diphenyl(2-pyridyl)phosphine) were synthesized by reacting anhydrous FeCl3 with respective ligand in acetonitrile solution under refluxing condition. Both the complexes were characterized by elemental analysis, FAB-Mass, FTIR, UV–Vis, ESR, Cyclic Voltammetry and magnetic measurement. The FAB mass spectra of complexes 1 and 2 show molecular ion peak at m/z 1078 [M]+ and m/z 687 [M−1]+, respectively, indicating mononuclear nature of the complexes. UV–Vis spectra of the complexes were consistent with low-spin, octahedral geometry. The variable temperature magnetic susceptibility measurement (73–323 K) of these complexes is also consistent with the paramagnetic nature of the complexes with a ground state spin S = ½. The Fe(III) centers of these two complexes remain low-spin, both at room temperature and liquid nitrogen temperature, was also indicated by the ESR analysis. Cyclic Voltammetry of both the complexes show an irreversible oxidation wave attributed to Fe3+ → Fe4+ + e− along with the peak for ligand oxidation. Theoretical calculations (B3LYP) of the complexes show that for complex 1, a trans geometry of the two phosphorous atoms and for complex 2, a mer,cis structures are the most favored geometrical isomer. TDDFT calculations were performed to interpret the observed bands in the UV–Visible spectra.

Two low-spin, mononuclear, Fe(III) complexes, with two P,N donor hemilabile ligands, were synthesized and characterized by elemental analysis, FAB-Mass, FTIR, UV–Vis, ESR, Cyclic Voltammetry and variable temperature magnetic measurements. Theoretical calculations (B3LYP) were performed to find out the most stable geometrical isomer of the complexes and also to interpret the UV–Vis spectra.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Inorganica Chimica Acta - Volume 362, Issue 14, 10 November 2009, Pages 5001–5011
نویسندگان
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