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 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 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 Fourier transform infrared spectra of the cluster anion[Cl2Fe2S2MoS2Cu(PPh3)2]- are measured between 550 and 90 cm(-1).The empirical assignments have been made for the vibration bands of main valence bonds.In orde...The Fourier transform infrared spectra of the cluster anion[Cl2Fe2S2MoS2Cu(PPh3)2]- are measured between 550 and 90 cm(-1).The empirical assignments have been made for the vibration bands of main valence bonds.In order to verify the assignments of the bands and obtain the force constants the approximate normal coordinate analysis for the title anion has been carried out.It is found that the calculated frequencies are in good agreement with the observed ones.While Quantum-Chemical calculation is used to elucidate the chemical bonding characteristics for the title anion.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 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
The title compound {Mo3 (μ3,-S) (μ-S)3 [μ-SOP (OEt )2] [S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of [Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldit...The title compound {Mo3 (μ3,-S) (μ-S)3 [μ-SOP (OEt )2] [S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of [Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldithiophosphate)and its structures was dctermined by X-ray crystallography. The crystal data for the title compound: triclinic, P1, Z= 2, a= 13. 011 (8), b= 13. 411 (9), c= 14. 385 (5)A, a=76. 59(5), B=78. 09(5), Y=82. 20(3), V= 2382(2) A3, Dc= 1.705 g/cm3, μ (MoKa) = 1. 434 mm-1, F (000) = 1228. The structure was refined to R =0.080 for 5485 observed reflections. Quasi-aromaticity in the puckered-ring of Mo3S3was experimentally probed by 31p NMR spectroscopic measurements. The 31p chemicalshifts of ligand DTP’s (diethyldithiophosphate) were modulated by the substituent effect of the adjacent bridging aromatic carboxylate through the long-distance super-conjugation via the trinuclear Mo cluster core.展开更多
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.
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 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.
文摘The Fourier transform infrared spectra of the cluster anion[Cl2Fe2S2MoS2Cu(PPh3)2]- are measured between 550 and 90 cm(-1).The empirical assignments have been made for the vibration bands of main valence bonds.In order to verify the assignments of the bands and obtain the force constants the approximate normal coordinate analysis for the title anion has been carried out.It is found that the calculated frequencies are in good agreement with the observed ones.While Quantum-Chemical calculation is used to elucidate the chemical bonding characteristics for the title anion.
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 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The title compound {Mo3 (μ3,-S) (μ-S)3 [μ-SOP (OEt )2] [S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of [Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldithiophosphate)and its structures was dctermined by X-ray crystallography. The crystal data for the title compound: triclinic, P1, Z= 2, a= 13. 011 (8), b= 13. 411 (9), c= 14. 385 (5)A, a=76. 59(5), B=78. 09(5), Y=82. 20(3), V= 2382(2) A3, Dc= 1.705 g/cm3, μ (MoKa) = 1. 434 mm-1, F (000) = 1228. The structure was refined to R =0.080 for 5485 observed reflections. Quasi-aromaticity in the puckered-ring of Mo3S3was experimentally probed by 31p NMR spectroscopic measurements. The 31p chemicalshifts of ligand DTP’s (diethyldithiophosphate) were modulated by the substituent effect of the adjacent bridging aromatic carboxylate through the long-distance super-conjugation via the trinuclear Mo cluster core.
