In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properti...In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.展开更多
A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic s...A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.展开更多
Two mononuclear tin(IV) complexes, [Sn(pda)2(edt)2] (pda = o-phenylenediamine) (C16H24N4S4Sn, Mr = 519.32) 1 and [Sn(eda)(edt)2] (eda = ethylenediamine) (C6H16N2S4Sn, Mr = 363.14) 2 were synthesized and characterized ...Two mononuclear tin(IV) complexes, [Sn(pda)2(edt)2] (pda = o-phenylenediamine) (C16H24N4S4Sn, Mr = 519.32) 1 and [Sn(eda)(edt)2] (eda = ethylenediamine) (C6H16N2S4Sn, Mr = 363.14) 2 were synthesized and characterized by X-ray structure analysis. 1 belongs to trigonal, space group P-3c1 with a = b = 20.0280(6), c = 8.7679(5) ? V = 3045.8(2) ?, Z = 6, Dc = 1.699 g/cm3, m = 1.677 mm-1, F(000) = 1572, the final R = 0.0418 and wR = 0.1019 for 1805 independent reflections. 2 crystallizes in monoclinic, space group P21/c with a = 10.911(3), b = 9.783(2), c = 11.831(3) ? b = 100.28(2), V = 1242.6(6) ?, Z = 4, Dc = 1.941 g/cm3, m = 2.690 mm-1, F(000) = 720, the final R = 0.0280 and wR = 0.0627 for 2166 independent reflections. Both Sn4+ ions in these two complexes are six-coordinated with a slightly distorted octahedral configu- ration.展开更多
文摘In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.
基金Project supported partly by the National Naural Science Foundation of China the Provincial Science Fund of Fujian.
文摘A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.
基金This research was financially supported by the grants from the State Key Laboratory of Structural Chemistry the National Science and Technology of China (001CB1089)+1 种基金 the Chinese Academy of Sciences (CAS) the National Science Foundation of China (20
文摘Two mononuclear tin(IV) complexes, [Sn(pda)2(edt)2] (pda = o-phenylenediamine) (C16H24N4S4Sn, Mr = 519.32) 1 and [Sn(eda)(edt)2] (eda = ethylenediamine) (C6H16N2S4Sn, Mr = 363.14) 2 were synthesized and characterized by X-ray structure analysis. 1 belongs to trigonal, space group P-3c1 with a = b = 20.0280(6), c = 8.7679(5) ? V = 3045.8(2) ?, Z = 6, Dc = 1.699 g/cm3, m = 1.677 mm-1, F(000) = 1572, the final R = 0.0418 and wR = 0.1019 for 1805 independent reflections. 2 crystallizes in monoclinic, space group P21/c with a = 10.911(3), b = 9.783(2), c = 11.831(3) ? b = 100.28(2), V = 1242.6(6) ?, Z = 4, Dc = 1.941 g/cm3, m = 2.690 mm-1, F(000) = 720, the final R = 0.0280 and wR = 0.0627 for 2166 independent reflections. Both Sn4+ ions in these two complexes are six-coordinated with a slightly distorted octahedral configu- ration.
