The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which...The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which consists of a discretecluster cation [Mo3S7 (S2P (iprO)2)3] + (ipr = isopropyl) and an anion [S2P (iprO)2]-It was synthesized from the reaction of (NH4)2MoS4 with HS2P (iprO)2. Crystallo-graphic data for its crystal: space group for 7356 independent reflec-'tions with The structure analysis reveals that the cation contains a typical(Mo3 (μ3,-S) (μ-S2)3]+ cluster core in which three molybdenum atoms form an isoscelestriangle;the structure of the free diisopropyldithiophosphate anion [S2P (iprO)2]- isdifferent obviously from the coordinated one.展开更多
The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = M...The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.展开更多
This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<...This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.展开更多
The binding energies of Mo,Cu,S and Br atoms in(NH4)2MoS4,[(n-Bu)4N]4[MoS4Cu6Br3] and [Mos4Cu6Br4(Py)4]n,were determined by usingXPS.The resul is revealed some eifferences in bonding properies ofthese three clusters.
The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethan...The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.展开更多
The cluster compound [Mo4S4 (μ-O2CC6H5)2(dtp)4] (dtp = S2P (OEt)2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo4S4(μ-dtp)2(dtp)4] in the mixed solvent of acetone, ethanol an...The cluster compound [Mo4S4 (μ-O2CC6H5)2(dtp)4] (dtp = S2P (OEt)2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo4S4(μ-dtp)2(dtp)4] in the mixed solvent of acetone, ethanol and water in the presence of C6H5CO2Na. It is monoclinic and crystallizesin space group C2/c, Mr =1495. 09, a=12. 175 (5) , b=22. 01 (1) , c=20.875(9) ,β=99. 04(4)°; V=5570(5) ; Z=4; Dc= 1. 78g/cm3;μ(MoKα) = 14. 52 cm-1; F(000) =2984. Final R factor is 0. 066. The result reveals that the [Mo4S4] cluster core and t-(dtp)1ligands are retained and onlyμ-bridged (dtp)1- ligands are substituted by (C6H5CO2)1in the substitution reaction, thus producing the title cluster compound,the structure of which contains two species of bidentate ligand.展开更多
The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffrac...The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.展开更多
Owing to the unique structural,electronic,and physico-chemical properties,molybdenum clusters are expected to play an important role in future nanotechnologies.However,their ground states are still under debate.In thi...Owing to the unique structural,electronic,and physico-chemical properties,molybdenum clusters are expected to play an important role in future nanotechnologies.However,their ground states are still under debate.In this study,the crystal structure analysis by particle swarm optimization(CALYPSO)approach is used for the global minimum search,which is followed by first-principles calculations,to detect an obvious dimerization tendency in Mo_(n)(n=2-18)clusters when the 4s and 4p semicore states are not regarded as the valence states.Further,the clusters with even number of atoms are usually magic clusters with high stability.However,after including the4 s and 4 p electrons as valence electrons,the dimerization tendency exhibits a drastic reduction because the average hybridization indices H_(sp),H_(sd),and H_(pd) are reduced significantly.Overall,this work reports new ground states of Mo_(n)(n=11,14,15)clusters and proves that semicore states are essential for Mo_(n) clusters.展开更多
The electronic structure and spectra of [Mo3O4-nSn]^(4+)(n=0-4) cations were calculated by means of INDO/CI quantum chemistry method to account for the experimental data of their spectra in water solutions.
Reaction of (NH_4)_2MoS_4 with AgI in α-MePy gives the title com- pound,an X-ray analysis of which shows that the molecule forms a one-dimensional polymeric chain with continuous metal-metal bonds.
Oxidation-reduction properties of some Fe-S and Mo-Fe-S clusters have been studied by cyclic voltammetric measurement. It is indicated that there are some factors which affect the oxidation- reduction properties of cl...Oxidation-reduction properties of some Fe-S and Mo-Fe-S clusters have been studied by cyclic voltammetric measurement. It is indicated that there are some factors which affect the oxidation- reduction properties of clusters, of which are charge density of metal atom in cluster core, electron effect of ligands, charge and geometric configurations of the reactant particle, etc.展开更多
The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen at...The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen atmosphere using standard Schlenk techniques. It gives rise to a novel 1D polymeric compound 1 with solvent MeCN coordinated to the copper atom. This situation is unprecedented in the W(Mo)/Cu/S system. The crystals were characterized by elemental analysis, IR and single-crystal X-ray crystallography. The configuration of the polymeric compound can be viewed as a helical chain which is propagated along the crystallographic c axis. The excited state absorption and refraction of compound 1 in CH3CN solution were studied by using the Z-scan technique with laser pulses of 40 ps pulse-width at a wavelength of 532 nm. The polymeric compound possesses an optical self-focusing performance. The positive nonlinear refraction is attributed to population transitions between singlet states. Compound 1 displays a strong excited-state absorption.展开更多
The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak inter...The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak interaction between the cluster anions through S atoms(μ-S or S of TDT ligands) in each unit cell of these two compounds.Moreover,the mutual transformation between these two compounds by the cluster reaction is discussed.Crystal data:for 1 space group=P1,a=12.996(4),b=18.100(8),c=12.530(4),α=91.57(3),β=97.42(3),γ=69.04(3)°,Z=2,5309 reflections,R=0.052;for 2 space group C2/c,a=26.504(9),b=22.177(5),c=17.355(9),β=108.43(9)°,Z=8,2999 reflections,R=0.079.展开更多
The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2<...The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2</sub>O）<sub>3</sub>] ZnBr4·4H<sub>2</sub>O was prepared by the redox reaction of Mo （CO）<sub>6</sub> with Na<sub>2</sub>W<sub>O</sub>4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334（4） , b= 9. 657（5） , c=19. 889（9） ,β= 139. 79 （5）°,V= 2026 （2） ￣3 , Z=2 , D<sub>c</sub>=2. 30 g/cm￣3 μ（MoKa） =106. 6 cm￣（-1） ,F（000）=1176 ,final R=0. 065 and R<sub>ω</sub>=0. 072 for 1964 reflections with I≥3σ（I）. In the structure of cation [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub> （H<sub>2</sub>O）<sub>3</sub>]￣（2+） molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.展开更多
文摘The title compound ttris-(diisopropyldithiophosphato)tris-μ-disulfidoμ3,-sulfido-cvclo-trimolybdenumj (3Mo-Mo) [diisopropyldithiophosphate], [Mo3S7 (S2P(iprO)2)3] [S2P(iprO)2] (Mr=1365. 39) is an ionic species which consists of a discretecluster cation [Mo3S7 (S2P (iprO)2)3] + (ipr = isopropyl) and an anion [S2P (iprO)2]-It was synthesized from the reaction of (NH4)2MoS4 with HS2P (iprO)2. Crystallo-graphic data for its crystal: space group for 7356 independent reflec-'tions with The structure analysis reveals that the cation contains a typical(Mo3 (μ3,-S) (μ-S2)3]+ cluster core in which three molybdenum atoms form an isoscelestriangle;the structure of the free diisopropyldithiophosphate anion [S2P (iprO)2]- isdifferent obviously from the coordinated one.
基金supported by CAS (SZD08002-2)973 Program (2007CB815306)+1 种基金the NNSFC (20733003 and 20673117)the Young Scientist’s Foundation of Fujian Province (2006F3136)
文摘The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.
文摘This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.
文摘The binding energies of Mo,Cu,S and Br atoms in(NH4)2MoS4,[(n-Bu)4N]4[MoS4Cu6Br3] and [Mos4Cu6Br4(Py)4]n,were determined by usingXPS.The resul is revealed some eifferences in bonding properies ofthese three clusters.
文摘The cluster compound[Mo_4S_4(μ-O_2CC_5H_5)_2(dtp)_4](dtp=S_2P(OEt)_2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo_4S_4(μ-dtp)_2(dtp)_4]in the mixed solvent of acetone,ethanol and water in the presence of C_6H_5CO_2Na.It is monoclinic and crystallizes in space group C2/c, Mr=1495.09,a=12.175(5),b=22.01(1),c=20.875(9),β=99.04(4)°;V=5575(5);Z=4; Dc=1.78g/cm^3.Final R factor is 0.066.The result reveals that the[Mo_4S_4]cluster core and t-(dtp)^(-1)ligands are retained and only μ-bridged(dtp)^(-1)ligands are substituted by(C_6H_5CO_2)^(-1)in the substitution reaction,thus producing the new title cluster compound,the structure of which contains two species of bidentate ligand.
文摘The cluster compound [Mo4S4 (μ-O2CC6H5)2(dtp)4] (dtp = S2P (OEt)2)was obtained by the ligand substitution reaction of tetranuclear molybdenum cluster [Mo4S4(μ-dtp)2(dtp)4] in the mixed solvent of acetone, ethanol and water in the presence of C6H5CO2Na. It is monoclinic and crystallizesin space group C2/c, Mr =1495. 09, a=12. 175 (5) , b=22. 01 (1) , c=20.875(9) ,β=99. 04(4)°; V=5570(5) ; Z=4; Dc= 1. 78g/cm3;μ(MoKα) = 14. 52 cm-1; F(000) =2984. Final R factor is 0. 066. The result reveals that the [Mo4S4] cluster core and t-(dtp)1ligands are retained and onlyμ-bridged (dtp)1- ligands are substituted by (C6H5CO2)1in the substitution reaction, thus producing the title cluster compound,the structure of which contains two species of bidentate ligand.
基金Work supported by the National Natural Science Foundation of China(NNSFC)
文摘The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.
基金supported by the National Natural Science Foundation of China (No.11404098 and No.11604082)the Student Research Training Program of Henan University of Science and Technology(WLSRTP201911)
文摘Owing to the unique structural,electronic,and physico-chemical properties,molybdenum clusters are expected to play an important role in future nanotechnologies.However,their ground states are still under debate.In this study,the crystal structure analysis by particle swarm optimization(CALYPSO)approach is used for the global minimum search,which is followed by first-principles calculations,to detect an obvious dimerization tendency in Mo_(n)(n=2-18)clusters when the 4s and 4p semicore states are not regarded as the valence states.Further,the clusters with even number of atoms are usually magic clusters with high stability.However,after including the4 s and 4 p electrons as valence electrons,the dimerization tendency exhibits a drastic reduction because the average hybridization indices H_(sp),H_(sd),and H_(pd) are reduced significantly.Overall,this work reports new ground states of Mo_(n)(n=11,14,15)clusters and proves that semicore states are essential for Mo_(n) clusters.
文摘The electronic structure and spectra of [Mo3O4-nSn]^(4+)(n=0-4) cations were calculated by means of INDO/CI quantum chemistry method to account for the experimental data of their spectra in water solutions.
文摘Reaction of (NH_4)_2MoS_4 with AgI in α-MePy gives the title com- pound,an X-ray analysis of which shows that the molecule forms a one-dimensional polymeric chain with continuous metal-metal bonds.
文摘Oxidation-reduction properties of some Fe-S and Mo-Fe-S clusters have been studied by cyclic voltammetric measurement. It is indicated that there are some factors which affect the oxidation- reduction properties of clusters, of which are charge density of metal atom in cluster core, electron effect of ligands, charge and geometric configurations of the reactant particle, etc.
基金Project (2005038557) supported by the Post-Doctor Programs Foundation of Ministry of Education of China
文摘The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen atmosphere using standard Schlenk techniques. It gives rise to a novel 1D polymeric compound 1 with solvent MeCN coordinated to the copper atom. This situation is unprecedented in the W(Mo)/Cu/S system. The crystals were characterized by elemental analysis, IR and single-crystal X-ray crystallography. The configuration of the polymeric compound can be viewed as a helical chain which is propagated along the crystallographic c axis. The excited state absorption and refraction of compound 1 in CH3CN solution were studied by using the Z-scan technique with laser pulses of 40 ps pulse-width at a wavelength of 532 nm. The polymeric compound possesses an optical self-focusing performance. The positive nonlinear refraction is attributed to population transitions between singlet states. Compound 1 displays a strong excited-state absorption.
文摘The crystal structures of two new trinuclear Mo-S cluster compounds[Mo3S7(TDT)3](Et4N)2·DMF1 and[Mo3S3(O)2(TDT)3](Et4N)2 2 with bianion TDT(S2C6H3CH32-) as ligands are reported in this paper.There is a weak interaction between the cluster anions through S atoms(μ-S or S of TDT ligands) in each unit cell of these two compounds.Moreover,the mutual transformation between these two compounds by the cluster reaction is discussed.Crystal data:for 1 space group=P1,a=12.996(4),b=18.100(8),c=12.530(4),α=91.57(3),β=97.42(3),γ=69.04(3)°,Z=2,5309 reflections,R=0.052;for 2 space group C2/c,a=26.504(9),b=22.177(5),c=17.355(9),β=108.43(9)°,Z=8,2999 reflections,R=0.079.
文摘The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2</sub>O）<sub>3</sub>] ZnBr4·4H<sub>2</sub>O was prepared by the redox reaction of Mo （CO）<sub>6</sub> with Na<sub>2</sub>W<sub>O</sub>4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334（4） , b= 9. 657（5） , c=19. 889（9） ,β= 139. 79 （5）°,V= 2026 （2） ￣3 , Z=2 , D<sub>c</sub>=2. 30 g/cm￣3 μ（MoKa） =106. 6 cm￣（-1） ,F（000）=1176 ,final R=0. 065 and R<sub>ω</sub>=0. 072 for 1964 reflections with I≥3σ（I）. In the structure of cation [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub> （H<sub>2</sub>O）<sub>3</sub>]￣（2+） molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.
