A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has bee...A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.展开更多
The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the '...The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the 'loose' ligands are determined. The crystallographic data of the cluster compounds with [W_3S_4]￣(4+) and [W_3CuS_4]￣(5+) cores are compared and their UV-Vis spectra are firstly reported. Thus, the 'quasi-aromaticity' of the [W_3S_4]￣(4+) core of these cluster compounds is discussed.展开更多
The reaction system of [Et4N]2MoSe4, FeCI2 and R2NCS2Na in DMF-CH3CN at ambient temperature yielded the Mo-Fe-Se cluster compounds MoFe3Se4(μ-R2NCS2)2(R2NCS2)4 (R2=Me2(1), Et2(2), C4H8(3)) with MoFe3Se4 core. X-ray d...The reaction system of [Et4N]2MoSe4, FeCI2 and R2NCS2Na in DMF-CH3CN at ambient temperature yielded the Mo-Fe-Se cluster compounds MoFe3Se4(μ-R2NCS2)2(R2NCS2)4 (R2=Me2(1), Et2(2), C4H8(3)) with MoFe3Se4 core. X-ray diffraction analyses of 2 revealed that the molecular structure contains a distorted cubane like M4Se4 core with two bridged and four chelated Et2NCS2- ligands. The cyclic voltammetric studies of the compounds showed the reversible mul-tielectron-transfer sequence.展开更多
A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group...A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.展开更多
In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monocli...In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.展开更多
The electronic structures of six cubane-like cluster compounds of the type[Fe_4S_4L_4]~n (L=SH,OH,and CI,n=-2 and -3;L=NO,n=0 and -1)have been calculated by using DV-X_α method,and the bonding properties are discusse...The electronic structures of six cubane-like cluster compounds of the type[Fe_4S_4L_4]~n (L=SH,OH,and CI,n=-2 and -3;L=NO,n=0 and -1)have been calculated by using DV-X_α method,and the bonding properties are discussed with emphasis on the ligand effect on cluster bonding. The comparisons of MO energies and cluster charge distributions with the experimental data are made, and the differences between the early studies and the present one are also briefly commented.展开更多
The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3....The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3. The structure contains a [W2CuAgS4](4+) distorted cubane-like core, Two types of metal-metal bonds exist in the core, One is W-W bond of which length is 0.2871(1) nm, the other is W-M' (M'=Cu or Ag) bends, whose mean distance is 0.2980 nm. The details of synthesis, structure, IR, UV-Vis and P-31 NMR spectra are reported. The crystallographic data are: space group P2(1)/n, with a=1.6987(4), b=1.7763(6), c=1.8918(5) nm, beta=98.54(2)degrees, V=5.645(3) nm(3), Z=4, and final R=0.043 for 6437 observed reflections.展开更多
文摘A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.
文摘The first successful attempt to prepare W_3S_4 {S_2P (OEt )_2}_4(H_2O) in organic phase is reported. Its substitution and addition reactions are investigated systematically, and the substitution sequences of the 'loose' ligands are determined. The crystallographic data of the cluster compounds with [W_3S_4]￣(4+) and [W_3CuS_4]￣(5+) cores are compared and their UV-Vis spectra are firstly reported. Thus, the 'quasi-aromaticity' of the [W_3S_4]￣(4+) core of these cluster compounds is discussed.
文摘The reaction system of [Et4N]2MoSe4, FeCI2 and R2NCS2Na in DMF-CH3CN at ambient temperature yielded the Mo-Fe-Se cluster compounds MoFe3Se4(μ-R2NCS2)2(R2NCS2)4 (R2=Me2(1), Et2(2), C4H8(3)) with MoFe3Se4 core. X-ray diffraction analyses of 2 revealed that the molecular structure contains a distorted cubane like M4Se4 core with two bridged and four chelated Et2NCS2- ligands. The cyclic voltammetric studies of the compounds showed the reversible mul-tielectron-transfer sequence.
基金Project supported by NNSFC and the Natural Science Foundation of Fujian.
文摘A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.
基金Project supported by the National Natural Science Foundation of Chinathe Climbing Program Foundation of China
文摘In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.
基金This work is financially supported by the National Natural Science Foundation of China.
文摘The electronic structures of six cubane-like cluster compounds of the type[Fe_4S_4L_4]~n (L=SH,OH,and CI,n=-2 and -3;L=NO,n=0 and -1)have been calculated by using DV-X_α method,and the bonding properties are discussed with emphasis on the ligand effect on cluster bonding. The comparisons of MO energies and cluster charge distributions with the experimental data are made, and the differences between the early studies and the present one are also briefly commented.
基金Project supported by the National Natural Science Foundation of China and the Foundation of the State Key Laboratory of Structural Chemistry.
文摘The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3. The structure contains a [W2CuAgS4](4+) distorted cubane-like core, Two types of metal-metal bonds exist in the core, One is W-W bond of which length is 0.2871(1) nm, the other is W-M' (M'=Cu or Ag) bends, whose mean distance is 0.2980 nm. The details of synthesis, structure, IR, UV-Vis and P-31 NMR spectra are reported. The crystallographic data are: space group P2(1)/n, with a=1.6987(4), b=1.7763(6), c=1.8918(5) nm, beta=98.54(2)degrees, V=5.645(3) nm(3), Z=4, and final R=0.043 for 6437 observed reflections.
