Under a suitable condition of crystallization, dark brown short rhombohedron crystals could be obtained from FeMoco-deficient MoFe protein (DeltanifE Avl) purified from a nifE deleted mutant DJ35 of Azotobacter vinela...Under a suitable condition of crystallization, dark brown short rhombohedron crystals could be obtained from FeMoco-deficient MoFe protein (DeltanifE Avl) purified from a nifE deleted mutant DJ35 of Azotobacter vinelandii Lipmann grown in NH3-limited medium. The number, size and quality of crystals were significantly affected by either the concentration of precipitants and buffer or diffusion method. The longest sides of the largest crystal of DeltanifE Avl protein, which was obtained by vapor diffusion in the hanging drop method, were 0.12 and 0.13 mm, respectively.展开更多
The heterotrinuclear cluster compound [MoW_2O_2 (O_2CC_2H_5 )_6-( H_2O)_3] ZnBr4·4H_2O was prepared by the redox reaction of Mo (CO)_6 with Na_2W_O4 in propionic anhydride. The crystal is monoclinic of space grou...The heterotrinuclear cluster compound [MoW_2O_2 (O_2CC_2H_5 )_6-( H_2O)_3] ZnBr4·4H_2O was prepared by the redox reaction of Mo (CO)_6 with Na_2W_O4 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_c=2. 30 g/cm￣3 μ(MoKa) =106. 6 cm￣(-1) ,F(000)=1176 ,final R=0. 065 and R_ω=0. 072 for 1964 reflections with I≥3σ(I). In the structure of cation [MoW_2O_2 (O_2CC_2H_5 )_6 (H_2O)_3]￣(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
The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10...The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.展开更多
A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure h...A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.展开更多
The dynamic recrystallization and carbides precipitation of the Cr-Co-Mo-Ni bearing steel were investigated by hot compression tests performed at temperatures ranging from 850 ℃to 1080 ℃ with strain rate of 1-20 s-1...The dynamic recrystallization and carbides precipitation of the Cr-Co-Mo-Ni bearing steel were investigated by hot compression tests performed at temperatures ranging from 850 ℃to 1080 ℃ with strain rate of 1-20 s-1. The activation energy（Q） for the tested steel is calculated to be around 682.99 k J/mol at a deformation strain of 0.6. Microstructural analysis by SEM shows that the dynamic recrystallization（DRX） behavior is dependent sensitively on the deformation strain, temperature and strain rate, while an exponential relationship between DRX grain size and Z parameter is obtained from the computational formula. Moreover, the M6C-type carbides（〈1 μm） act as the main prohibitor of grain coarsening, and the polynomial regression relationship between them is worked out. With electron backscatter diffraction（EBSD） observation, DRX is the main nucleation mechanism responsible for the formation of new grains during hot compression. In conclusion, the interaction between DRX affected by hot deformation parameters and carbides precipitation determines the ultimate grain size refinement.展开更多
The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C...The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C23H16O9N4MoNiRuS, Mr = 780.18, orthorhombic, space group Pbca with the following crystallographic parameters: a = 13.207(4), b = 16.036(5), c = 25.513(8) , Z = 8, V = 5403(3) 3, Dc = 1.918 g/cm3, m = 1.834 mm-1 and F(000) = 3072. The final R = 0.0512 and wR = 0.1132 for 2525 reflections with I > 2.00s(I).展开更多
The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=289...The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=2890 (3) A3, Z=2, A = 2. 08 g/cm3, F(000) -1780, Final R = 0. 049, Rw = 0. 058 for 2622 independent reflectons with I>3σ(I). The complex anion contains two Mo3O4 cores which connect two chromium atoms through four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atoms and the Mo atoms is coordinated by six oxygen atoms. The anions are linked by Na cations to form one-dimensional infinite chain structure.展开更多
The hetero-metal clusters [■5-C5H4C（O）CH2CH2C（O）OCH3]FeCoM（■3-S）（CO）8 （M = Mo 1, M = W 2） were prepared by thermal reactions of FeCo2（CO）9(（3-S） with metal exchange reagent [■5-C5H4C（O）CH2CH2C（O）O...The hetero-metal clusters [■5-C5H4C（O）CH2CH2C（O）OCH3]FeCoM（■3-S）（CO）8 （M = Mo 1, M = W 2） were prepared by thermal reactions of FeCo2（CO）9(（3-S） with metal exchange reagent [■5-C5H4C（O）CH2CH2C（O）OCH3]M（CO）3Na （M = Mo or W） in THF. Cluster 1 reacted with 2,4-dinitrophenylhydrazine at room temperature to yield the cluster hydrazone derivative (（3-S）CoFeMo（CO）8[(5-C5H4C（NR）Me] [R = NHC6H3-2,4-（NO2）2] 3. All the compounds were characterized by elemental analyses, IR and NMR spectra. Cluster 1 was determined by single crystal X-ray diffraction. Crystal data: C18H11O11SCoFeMo, Mr = 646.05, triclinic, space group P, a = 8.148（2）, b = 10.685（3）, c = 13.410（4） ?, ( = 100.077（5）, ( = 102.452（5）, ( = 91.108（6）(, V = 1120.4（5） ?3, Z = 2, Dc = 1.915 g/cm3, F（000） = 636, ( = 2.071 mm(1, the final R = 0.0378 and wR = 0.0968 for 5074 observations with (I > 2（（I））.展开更多
The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a ...The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a = 9.135(1), b = 9.772(1), c = 17.000(2) , a = 76.377(2), b = 78.333(2), g = 67.243(2)? Mr = 582.44, V = 1349.7(3) 3, Z = 2, Dc = 1.433 g/cm3, m(MoKa) = 0.581 mm-1 and F(000) = 596. A total of 5614 reflections were collected in the range of 2.30< q < 25.03? of which 4721 were independent (Rint = 0.0176) and 4159 observed reflections (I ≥ 2s(I)) were used in the refinement. R = 0.0326 and wR = 0.0867. The Mo centre is six-coordinated by four carbonyls (MoC 1.938(4), 2.003(4), 2.019(4), 2.035(4) ) and P, N atoms from the ligand (MoP 2.4812(8), MoN 2.349(3) ?. The coordination geometry of the complex can be described as an octahedron.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
The reaction of μ alkyne bridged dimolybdenum compound 〔Mo 2( μ C 2HPh)(CO) 4( η 5 C 5H 4C(O)Me) 2〕 1 with Co 2(CO) 8 in refluxing toluene gave a new butterfly compound 〔Co 2Mo 2( μ 4 C 2HPh)( μ CO) 4(CO) 4( ...The reaction of μ alkyne bridged dimolybdenum compound 〔Mo 2( μ C 2HPh)(CO) 4( η 5 C 5H 4C(O)Me) 2〕 1 with Co 2(CO) 8 in refluxing toluene gave a new butterfly compound 〔Co 2Mo 2( μ 4 C 2HPh)( μ CO) 4(CO) 4( η 5 C 5H 4C(O)Me) 2〕 2 which was fully characterized by elemental analysis, IR, 1H NMR and X ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C 30 H 20 Co 2Mo 2O 10 , M r =850.23, space group P2 1/a(#14), a=14.165(5), b=12.498(2), c=16.204(2) , β = 96 50(2)°, V = 2850(1) 3, Z = 4, D c = 1.981 g cm -3 , F(000)=1672, μ (Mo Kα )=20.41 cm -1 , final R=0.030, R w =0.039 for 4831 observable reflections with I>2σ(I ). The structure contains a Co 2Mo 2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi bridging carbonyl 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 cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc...The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.展开更多
A brown-red compound [( PPh_3 )_2Cu_2MoOS_3] was synthesized through a solid state reaction. The crystal is monoclinic, space group P2_1/c with α =19. 316(5), b=10. 46(1), c=24. 738(8) A, β=97. 01(2)°, V=4946(9...A brown-red compound [( PPh_3 )_2Cu_2MoOS_3] was synthesized through a solid state reaction. The crystal is monoclinic, space group P2_1/c with α =19. 316(5), b=10. 46(1), c=24. 738(8) A, β=97. 01(2)°, V=4946(9) A￣3, Z=4. The unique Mo atom has a distorted tetrahedral coordination geometry, one Cu atom has a distorted tetrahedral coordination geometry, too, but the other has a trigonal planar environment. The core , Cu_2MoOS_3, shows a butterfly-like structure.展开更多
文摘Under a suitable condition of crystallization, dark brown short rhombohedron crystals could be obtained from FeMoco-deficient MoFe protein (DeltanifE Avl) purified from a nifE deleted mutant DJ35 of Azotobacter vinelandii Lipmann grown in NH3-limited medium. The number, size and quality of crystals were significantly affected by either the concentration of precipitants and buffer or diffusion method. The longest sides of the largest crystal of DeltanifE Avl protein, which was obtained by vapor diffusion in the hanging drop method, were 0.12 and 0.13 mm, respectively.
文摘The heterotrinuclear cluster compound [MoW_2O_2 (O_2CC_2H_5 )_6-( H_2O)_3] ZnBr4·4H_2O was prepared by the redox reaction of Mo (CO)_6 with Na_2W_O4 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_c=2. 30 g/cm￣3 μ(MoKa) =106. 6 cm￣(-1) ,F(000)=1176 ,final R=0. 065 and R_ω=0. 072 for 1964 reflections with I≥3σ(I). In the structure of cation [MoW_2O_2 (O_2CC_2H_5 )_6 (H_2O)_3]￣(2+) molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.
基金The paper is financially supported by NSF of Fujian Province (JA00137) by FPNSFC(E0110013)
文摘The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.
基金This work was financially supported by the NNSF of China (No. 29733090 and No. 20173063) Key Project in KIP of CAS (KJCX2-H3) and the NNSF of Fujian Province (E0020001)
文摘A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.
基金Project(2012AA03A503) supported by the National High Technology Research and Development Program of China
文摘The dynamic recrystallization and carbides precipitation of the Cr-Co-Mo-Ni bearing steel were investigated by hot compression tests performed at temperatures ranging from 850 ℃to 1080 ℃ with strain rate of 1-20 s-1. The activation energy（Q） for the tested steel is calculated to be around 682.99 k J/mol at a deformation strain of 0.6. Microstructural analysis by SEM shows that the dynamic recrystallization（DRX） behavior is dependent sensitively on the deformation strain, temperature and strain rate, while an exponential relationship between DRX grain size and Z parameter is obtained from the computational formula. Moreover, the M6C-type carbides（〈1 μm） act as the main prohibitor of grain coarsening, and the polynomial regression relationship between them is worked out. With electron backscatter diffraction（EBSD） observation, DRX is the main nucleation mechanism responsible for the formation of new grains during hot compression. In conclusion, the interaction between DRX affected by hot deformation parameters and carbides precipitation determines the ultimate grain size refinement.
基金This work was supported by the National Natural Science Foundation of China
文摘The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C23H16O9N4MoNiRuS, Mr = 780.18, orthorhombic, space group Pbca with the following crystallographic parameters: a = 13.207(4), b = 16.036(5), c = 25.513(8) , Z = 8, V = 5403(3) 3, Dc = 1.918 g/cm3, m = 1.834 mm-1 and F(000) = 3072. The final R = 0.0512 and wR = 0.1132 for 2525 reflections with I > 2.00s(I).
文摘The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=2890 (3) A3, Z=2, A = 2. 08 g/cm3, F(000) -1780, Final R = 0. 049, Rw = 0. 058 for 2622 independent reflectons with I>3σ(I). The complex anion contains two Mo3O4 cores which connect two chromium atoms through four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atoms and the Mo atoms is coordinated by six oxygen atoms. The anions are linked by Na cations to form one-dimensional infinite chain structure.
基金the National Natural Science Foundation of China.
文摘The hetero-metal clusters [■5-C5H4C（O）CH2CH2C（O）OCH3]FeCoM（■3-S）（CO）8 （M = Mo 1, M = W 2） were prepared by thermal reactions of FeCo2（CO）9(（3-S） with metal exchange reagent [■5-C5H4C（O）CH2CH2C（O）OCH3]M（CO）3Na （M = Mo or W） in THF. Cluster 1 reacted with 2,4-dinitrophenylhydrazine at room temperature to yield the cluster hydrazone derivative (（3-S）CoFeMo（CO）8[(5-C5H4C（NR）Me] [R = NHC6H3-2,4-（NO2）2] 3. All the compounds were characterized by elemental analyses, IR and NMR spectra. Cluster 1 was determined by single crystal X-ray diffraction. Crystal data: C18H11O11SCoFeMo, Mr = 646.05, triclinic, space group P, a = 8.148（2）, b = 10.685（3）, c = 13.410（4） ?, ( = 100.077（5）, ( = 102.452（5）, ( = 91.108（6）(, V = 1120.4（5） ?3, Z = 2, Dc = 1.915 g/cm3, F（000） = 636, ( = 2.071 mm(1, the final R = 0.0378 and wR = 0.0968 for 5074 observations with (I > 2（（I））.
基金This work was supported by the National Natural Science Foundation of China (No. 20102003)
文摘The crystal structure of the title complex, Mo(CO)4(NNP), (NNP=2-(N-cyclohexyl- N-diphenylphosphinomethyl)aminopyridine) has been determined, and its crystallographic data are as follows: triclinic, space group P , a = 9.135(1), b = 9.772(1), c = 17.000(2) , a = 76.377(2), b = 78.333(2), g = 67.243(2)? Mr = 582.44, V = 1349.7(3) 3, Z = 2, Dc = 1.433 g/cm3, m(MoKa) = 0.581 mm-1 and F(000) = 596. A total of 5614 reflections were collected in the range of 2.30< q < 25.03? of which 4721 were independent (Rint = 0.0176) and 4159 observed reflections (I ≥ 2s(I)) were used in the refinement. R = 0.0326 and wR = 0.0867. The Mo centre is six-coordinated by four carbonyls (MoC 1.938(4), 2.003(4), 2.019(4), 2.035(4) ) and P, N atoms from the ligand (MoP 2.4812(8), MoN 2.349(3) ?. The coordination geometry of the complex can be described as an octahedron.
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.
文摘The reaction of μ alkyne bridged dimolybdenum compound 〔Mo 2( μ C 2HPh)(CO) 4( η 5 C 5H 4C(O)Me) 2〕 1 with Co 2(CO) 8 in refluxing toluene gave a new butterfly compound 〔Co 2Mo 2( μ 4 C 2HPh)( μ CO) 4(CO) 4( η 5 C 5H 4C(O)Me) 2〕 2 which was fully characterized by elemental analysis, IR, 1H NMR and X ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C 30 H 20 Co 2Mo 2O 10 , M r =850.23, space group P2 1/a(#14), a=14.165(5), b=12.498(2), c=16.204(2) , β = 96 50(2)°, V = 2850(1) 3, Z = 4, D c = 1.981 g cm -3 , F(000)=1672, μ (Mo Kα )=20.41 cm -1 , final R=0.030, R w =0.039 for 4831 observable reflections with I>2σ(I ). The structure contains a Co 2Mo 2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi bridging carbonyl 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.
文摘The cubane-type mixed Mo W cluster[Mo2W2S4 (OAc)2(dtp)3 (dtpH)]·CH2Cl2 (dtp= (EtO)2PS2, dtpH = (EtO)2PS (SH) has been prepared by reduction and addition reaction between dinuclear W2S4 (dtp)2 and Mo(CO)6 in HOAc and Ac2O solution in the presence of dtp-ligand. Crystallographic data: Mr=1632. 71,monoclinic, space group P2/n, a=13. 146 (8), b=11. 961 (5),c=17. 157 (9) β =105. 99(8)°, V=2593(8), Z=2, Dc=2. 09 /cm￣3 ,λ(MoKa) =0.71073 ,F (000)=1578, final R=0. 029, Rw = 0. 041 for 3765 unique intensity data [I≥4σ (I)]. The result of X-ray study and elemental analysis indicated that, in the crystal lattice, molybdenum and tungsten are statistically distributed in the metal positions each with 0. 5 fractional occupation.
文摘A brown-red compound [( PPh_3 )_2Cu_2MoOS_3] was synthesized through a solid state reaction. The crystal is monoclinic, space group P2_1/c with α =19. 316(5), b=10. 46(1), c=24. 738(8) A, β=97. 01(2)°, V=4946(9) A￣3, Z=4. The unique Mo atom has a distorted tetrahedral coordination geometry, one Cu atom has a distorted tetrahedral coordination geometry, too, but the other has a trigonal planar environment. The core , Cu_2MoOS_3, shows a butterfly-like structure.
