Reaction of(NH 4) 2MoOS 3 with CuBr and AgBr(molar ratio=1∶4∶1) in α-MePy produced dark red crystals of [MoOS 3Cu 4(α-MePy) 6Br 2]. The product was characterized by elemental analysis, IR and X-ray diffraction. It...Reaction of(NH 4) 2MoOS 3 with CuBr and AgBr(molar ratio=1∶4∶1) in α-MePy produced dark red crystals of [MoOS 3Cu 4(α-MePy) 6Br 2]. The product was characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in a triclinic system with space group P1 and unit cell parameters a=0.950 9(3) nm, b=1.066 8(2) nm, c=2.153 6(3) nm, α=94.846(9)°, β=92.054(7)°, γ=99.299(8)°, V=2.145 5(8) nm 3, Z=2, D c=1.828 g·cm -3, F(000)=1 168, μ=42.79 cm -1, R=0.049 and R w=0.051. The compound consists of a nido-shaped MoS 3Cu 3 cluster unit and a four-membered CuBrCuS ring by sharing the same Cu3—S3 bond. The Mo atom and the four Cu atoms adopt a distorted tetrahedral geometry coordination. The Mo…Cu1, Mo…Cu2 and Mo…Cu3 distances are 0.271 1(3), 0 269 8(2), and 0.268 1(1) nm, respectively.展开更多
The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in th...The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.展开更多
A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes...A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.展开更多
In this work, with the analysis on MO and electronic structure for a series of heteronuclear cluster with cubane type (Mo4S1 )xMn1(x=1.2. M = Cu, W, Ni, Sb, Mo, Sn, Cu2) we found that it is with the multiple center d-...In this work, with the analysis on MO and electronic structure for a series of heteronuclear cluster with cubane type (Mo4S1 )xMn1(x=1.2. M = Cu, W, Ni, Sb, Mo, Sn, Cu2) we found that it is with the multiple center d-pir orbitals that the ligand Mo3S44+ bonds to the M atom to form these class clusters. It is revealed that the charges transfer from the M atom to Mo atom of the ligand Mo3S44+ and its relationship with the MC (multiple center) d-pπ orbitals. Based on the charge transfer the electronic spectrum and the magnetic property of some cubane clusters have been discussed.展开更多
The syntheses and structures of trinuclear Mo (W)-Fe-S cluster[MFe2S2(CO)8 (S,CNSEt2)]- (M=Mo, W), hexanuclear Fe-S cluster [Fe6S6-(CO)12]2- and undecanuclear Cu-Fe-S cluster [Cu5Fe6S6(CO)18(PPh3)2]-, containingFe2S2(...The syntheses and structures of trinuclear Mo (W)-Fe-S cluster[MFe2S2(CO)8 (S,CNSEt2)]- (M=Mo, W), hexanuclear Fe-S cluster [Fe6S6-(CO)12]2- and undecanuclear Cu-Fe-S cluster [Cu5Fe6S6(CO)18(PPh3)2]-, containingFe2S2(CO)6-units bave been summarized and the important vestiges left in their struc-tures reflecting the formation processes of the clusters have been found and discussed.Further inspecting some other typical clusters a regular unit construction in the forma-tion of the metal cluster compounds containing Fe2S2(CO)6-units has been figured outand applied to speculate and predict several new cluster compounds containing Fe2S2(CO)6-units.展开更多
文摘Reaction of(NH 4) 2MoOS 3 with CuBr and AgBr(molar ratio=1∶4∶1) in α-MePy produced dark red crystals of [MoOS 3Cu 4(α-MePy) 6Br 2]. The product was characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in a triclinic system with space group P1 and unit cell parameters a=0.950 9(3) nm, b=1.066 8(2) nm, c=2.153 6(3) nm, α=94.846(9)°, β=92.054(7)°, γ=99.299(8)°, V=2.145 5(8) nm 3, Z=2, D c=1.828 g·cm -3, F(000)=1 168, μ=42.79 cm -1, R=0.049 and R w=0.051. The compound consists of a nido-shaped MoS 3Cu 3 cluster unit and a four-membered CuBrCuS ring by sharing the same Cu3—S3 bond. The Mo atom and the four Cu atoms adopt a distorted tetrahedral geometry coordination. The Mo…Cu1, Mo…Cu2 and Mo…Cu3 distances are 0.271 1(3), 0 269 8(2), and 0.268 1(1) nm, respectively.
文摘The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.
文摘A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.
文摘In this work, with the analysis on MO and electronic structure for a series of heteronuclear cluster with cubane type (Mo4S1 )xMn1(x=1.2. M = Cu, W, Ni, Sb, Mo, Sn, Cu2) we found that it is with the multiple center d-pir orbitals that the ligand Mo3S44+ bonds to the M atom to form these class clusters. It is revealed that the charges transfer from the M atom to Mo atom of the ligand Mo3S44+ and its relationship with the MC (multiple center) d-pπ orbitals. Based on the charge transfer the electronic spectrum and the magnetic property of some cubane clusters have been discussed.
文摘The syntheses and structures of trinuclear Mo (W)-Fe-S cluster[MFe2S2(CO)8 (S,CNSEt2)]- (M=Mo, W), hexanuclear Fe-S cluster [Fe6S6-(CO)12]2- and undecanuclear Cu-Fe-S cluster [Cu5Fe6S6(CO)18(PPh3)2]-, containingFe2S2(CO)6-units bave been summarized and the important vestiges left in their struc-tures reflecting the formation processes of the clusters have been found and discussed.Further inspecting some other typical clusters a regular unit construction in the forma-tion of the metal cluster compounds containing Fe2S2(CO)6-units has been figured outand applied to speculate and predict several new cluster compounds containing Fe2S2(CO)6-units.
