This paper studies the small molybdenum clusters of Mon （n=2 8） and their adsorption of N2 molecule by using the density functional theory （DFT） with the generalized gradient approximation. The optimized structure...This paper studies the small molybdenum clusters of Mon （n=2 8） and their adsorption of N2 molecule by using the density functional theory （DFT） with the generalized gradient approximation. The optimized structures of Mon clusters show the onset of a structural transition from a close-packed structure towards a body-centred cubic structure occurred at n = 7. An analysis of adsorption energies suggests that the Mo2 is of high inertness and Mo6 cluster is of high activity against the adsorption of N2. Calculated results indicate that the N2 molecule prefers end-on mode by forming a linear or quasi-linear structure Mo-N-N, and the adsorption of nitrogen on molybdenum clusters is molecular adsorption with slightly elongated N-N bond. The electron density of highest occupied molecular orbital and lowest unoccupied molecular orbital, and the partial density of states of representative cluster are also used to characterize the adsorption properties of N2 on the sized Mon clusters.展开更多
通过酶动力学方法考察了轮型钼簇(Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6)对α-葡萄糖苷酶的抑制效果、抑制机理和抑制类型。结果表明:Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6对α-葡萄糖苷酶均有较好的抑制效果,其中Mo 57 Fe 6...通过酶动力学方法考察了轮型钼簇(Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6)对α-葡萄糖苷酶的抑制效果、抑制机理和抑制类型。结果表明:Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6对α-葡萄糖苷酶均有较好的抑制效果,其中Mo 57 Fe 6对α-葡萄糖苷酶的抑制效果最好,其IC 50=(0.0259±0.000328)mmol/L;Mo 36对α-葡萄糖苷酶的抑制作用为可逆竞争型抑制,Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6的抑制作用为可逆混合型抑制。展开更多
Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 ...Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 1/c, with lattice parameters a=1.17383(4) nm, b=2.40136(4) nm, c=2.64112(5) nm, β=94.2020(5)°, V=7.4247(5) nm 3 and Z=4. The structure of the [MoS 4Cu 5Br 6] 3- trianion of 1 is composed of one nido-like [MoS 3Cu 3] core and one half-open cubane-like [MoS 3Cu 3Br] core, which are interconnected by sharing the same MoSCuS plane. The Mo...Cu distances vary in the range of 0.2622(6)-0.2692(5) nm.展开更多
Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 ...Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. In the structure of 2, the cluster core MoS4Cu2 of the cluster precursor 1 is retained and serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D （6,3） （honeycomb-like） network. The acetic acid induced aggregation of supramolecular compound 2 from the cluster precursor 1 suggests that this simple synthetic strategy be likely applicable to many related systems.展开更多
The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21...The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.展开更多
A series of carboxylate-substituted trinuclear molybdenum cluster compounds formulated as Mo 3S 4(DTP) 3(RCO 2)(L), where R=H, CH 3, C 2H 5, CH 2Cl, CCl 3, R 1C 6H 4 (R 1 is the group on the benzene ring ...A series of carboxylate-substituted trinuclear molybdenum cluster compounds formulated as Mo 3S 4(DTP) 3(RCO 2)(L), where R=H, CH 3, C 2H 5, CH 2Cl, CCl 3, R 1C 6H 4 (R 1 is the group on the benzene ring of aromatic carboxylate), L=pyridine, CH 3CN, DMF, have been synthesized by the ligand substitution reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by 31P NMR. The dissociation process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution structure and reactive properties of the cluster. The long-distance interaction between ligands RCO 2 and L is transported by Mo 3S 4 core.展开更多
Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2?6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2?(DMSO)2?(Et2O) 1 (C88H86...Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2?6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2?(DMSO)2?(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) ?, β = 92.835o, V = 9829.3(3) ?3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co–N and Mo…Mo bond distances are 2.139 and 2.872 ?, respectively.展开更多
A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belong...A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.展开更多
A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC... A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.展开更多
Two triangular molybdenum-tellurium clusters, Mo_3Te_7-[S_2CN(CH_2CH_2OH)_2]_3I (1) and Mo_3Te_4Y_3[S_2P(~iPrO)_2]_3I (Y_3 = 1. 43Te+ 1.57S) (2), were obtainedfrom the reaction of K·HOdtc [HOdtc = S_2CN(CH_2CH_2O...Two triangular molybdenum-tellurium clusters, Mo_3Te_7-[S_2CN(CH_2CH_2OH)_2]_3I (1) and Mo_3Te_4Y_3[S_2P(~iPrO)_2]_3I (Y_3 = 1. 43Te+ 1.57S) (2), were obtainedfrom the reaction of K·HOdtc [HOdtc = S_2CN(CH_2CH_2OH)_2] or K·~iPr_2dtp (~iPr_2dtp =S_2P[OCH(CH_3)_2]_2) with a mixed product of elements Mo, Te(S) and I_2 at high temperature. Thestructures of the two compounds were determined by X-ray crystallography study. Crystal data are,(1): monoclinic, P2_1/n, a = 1.6256(3), b = 1.3264(2), c = 1.8808(4) nm, β = 96.923°, V = 4.025.9(14) nm^3, D_(cal) = 3.050 g·cm^(-3), Z = 4, and (2): monoclinic, P2_1/n = 1.4564(2), b =2.3917(4), c = 1.5094(3) nm, β= 114.35(2)°, V = 4.0259(14) nm^3, D_(cal) = 2.449 g·cm^(-3) and Z= 4. Single crystal analyses show that 1 consists of discrete Mo_3Te_7[S_2CN(CH_2CH_2OH)_2]_3Iconnected into three-dimensional framework via hydrogen bonds, while 2 forms a linear chain viaTe(S)―I interaction.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant No. 10964012)the Prior Developing Subject Foundation of Xinjiang Normal University
文摘This paper studies the small molybdenum clusters of Mon （n=2 8） and their adsorption of N2 molecule by using the density functional theory （DFT） with the generalized gradient approximation. The optimized structures of Mon clusters show the onset of a structural transition from a close-packed structure towards a body-centred cubic structure occurred at n = 7. An analysis of adsorption energies suggests that the Mo2 is of high inertness and Mo6 cluster is of high activity against the adsorption of N2. Calculated results indicate that the N2 molecule prefers end-on mode by forming a linear or quasi-linear structure Mo-N-N, and the adsorption of nitrogen on molybdenum clusters is molecular adsorption with slightly elongated N-N bond. The electron density of highest occupied molecular orbital and lowest unoccupied molecular orbital, and the partial density of states of representative cluster are also used to characterize the adsorption properties of N2 on the sized Mon clusters.
文摘通过酶动力学方法考察了轮型钼簇(Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6)对α-葡萄糖苷酶的抑制效果、抑制机理和抑制类型。结果表明:Mo 36、Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6对α-葡萄糖苷酶均有较好的抑制效果,其中Mo 57 Fe 6对α-葡萄糖苷酶的抑制效果最好,其IC 50=(0.0259±0.000328)mmol/L;Mo 36对α-葡萄糖苷酶的抑制作用为可逆竞争型抑制,Mo 57 Mn 6、Mo 57 V 6、Mo 57 Fe 6的抑制作用为可逆混合型抑制。
基金theKeyLaboratoryofOrganicChemistryofJiangsuProvince (No .KJS0 1017)andtheStateKeyLaboratoryofCoordinationChemistryofNanjingUniversity
文摘Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 1/c, with lattice parameters a=1.17383(4) nm, b=2.40136(4) nm, c=2.64112(5) nm, β=94.2020(5)°, V=7.4247(5) nm 3 and Z=4. The structure of the [MoS 4Cu 5Br 6] 3- trianion of 1 is composed of one nido-like [MoS 3Cu 3] core and one half-open cubane-like [MoS 3Cu 3Br] core, which are interconnected by sharing the same MoSCuS plane. The Mo...Cu distances vary in the range of 0.2622(6)-0.2692(5) nm.
基金Project supported by the National Natural Science Foundation of China （No. 20271036）, the Natural Science Foundation of Jiangsu Province （No. BK2004205）, the Natural Science Foundation of the Education Committee of Jiangsu Province （No. 03KJD 150241 ）, and the Key Laboratory of 0rganic Synthesis of Jiangsu Province （No. JSK001 ） in China.
文摘Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. In the structure of 2, the cluster core MoS4Cu2 of the cluster precursor 1 is retained and serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D （6,3） （honeycomb-like） network. The acetic acid induced aggregation of supramolecular compound 2 from the cluster precursor 1 suggests that this simple synthetic strategy be likely applicable to many related systems.
基金The project was supported by the NNSFC (No. 20525101)the NSF of Jiangsu Province (No. BK2004205)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20050285004)the State Key Laboratory of Organometallic Chemistry (No. 06-26)
文摘The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.
文摘A series of carboxylate-substituted trinuclear molybdenum cluster compounds formulated as Mo 3S 4(DTP) 3(RCO 2)(L), where R=H, CH 3, C 2H 5, CH 2Cl, CCl 3, R 1C 6H 4 (R 1 is the group on the benzene ring of aromatic carboxylate), L=pyridine, CH 3CN, DMF, have been synthesized by the ligand substitution reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by 31P NMR. The dissociation process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution structure and reactive properties of the cluster. The long-distance interaction between ligands RCO 2 and L is transported by Mo 3S 4 core.
基金This work was supported by the NNSFC (No. 20271036), the NSF of Jiangsu Province (No. BK2004205) and the State Key Laboratory of Structural Chemistry (030066)
文摘Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2?6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2?(DMSO)2?(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) ?, β = 92.835o, V = 9829.3(3) ?3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co–N and Mo…Mo bond distances are 2.139 and 2.872 ?, respectively.
基金This work was supported by the State Key Basic Research and Development Plan of China (001CB108906)the YIF (2005J060) and NSF (2006J0015) of Fujian Provincethe Major Special Foundation of Fujian Province (2005HZ1027 and 2005HZ01-1)
文摘A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.
基金Project supported by the State Key Laboratory of Structural Chemistry and the National Natural Science Foundation of China
文摘 A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 730 48)andtheNaturalScienceFoundationofFujianProvince China
文摘Two triangular molybdenum-tellurium clusters, Mo_3Te_7-[S_2CN(CH_2CH_2OH)_2]_3I (1) and Mo_3Te_4Y_3[S_2P(~iPrO)_2]_3I (Y_3 = 1. 43Te+ 1.57S) (2), were obtainedfrom the reaction of K·HOdtc [HOdtc = S_2CN(CH_2CH_2OH)_2] or K·~iPr_2dtp (~iPr_2dtp =S_2P[OCH(CH_3)_2]_2) with a mixed product of elements Mo, Te(S) and I_2 at high temperature. Thestructures of the two compounds were determined by X-ray crystallography study. Crystal data are,(1): monoclinic, P2_1/n, a = 1.6256(3), b = 1.3264(2), c = 1.8808(4) nm, β = 96.923°, V = 4.025.9(14) nm^3, D_(cal) = 3.050 g·cm^(-3), Z = 4, and (2): monoclinic, P2_1/n = 1.4564(2), b =2.3917(4), c = 1.5094(3) nm, β= 114.35(2)°, V = 4.0259(14) nm^3, D_(cal) = 2.449 g·cm^(-3) and Z= 4. Single crystal analyses show that 1 consists of discrete Mo_3Te_7[S_2CN(CH_2CH_2OH)_2]_3Iconnected into three-dimensional framework via hydrogen bonds, while 2 forms a linear chain viaTe(S)―I interaction.
