The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-m...The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-methoxylbenzoic acid and p-hydroxybenzoic acid, respectively. Their crystal structures were determined by X-ray diffraction analysis. The crystal data for compound 1: Mo3S10P3C25H42O9N, monoclinic P21/n, Mr = 1201.93, Z = 4, a = 14.164(1), b = 23.065(2), c = 14.732(1) ? = 109.677(1) ? V = 4532(1) ?, D= 1.762 gcm-3, = 1.428 mm-1, F (000) = 2408, R = 0.0739, wR = 0.1528 for 3552 observed reflections (I > 2); and for compound 2: Mo3S10P3C24H48O11N, triclinic P ? Mr = 1227.96, Z = 2, = 10.2098(3), b = 14.3333(4), c = 18.1711(5) ? = 94.694(1), = 102.166(1), = 110.665(1) , V = 2396.5(1)3, Dc = 1.638 gcm-3, = 1.350mm-1, F (000) = 1184, R = 0.0445, wR = 0.1281 for 6597 observed reflections (I > 2). Intermolecular S…S interactions are observed between the molecules of compound 1 while intramolecular O…HC and intermolecular S…HC hydrogen bondings are found in the crystal packing diagram of compound 2.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 The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.展开更多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 reactions of [(h5-C5Me5)Mo(StBu)3] with equimolar FeBr3 in THF afforded a neutral tetranuclear cluster [(h5-C5Me5)2Mo2Fe2S4Br2] 1. The structure of 1 was determined by single-crystal X-ray diffraction analysis. 1 ...The reactions of [(h5-C5Me5)Mo(StBu)3] with equimolar FeBr3 in THF afforded a neutral tetranuclear cluster [(h5-C5Me5)2Mo2Fe2S4Br2] 1. The structure of 1 was determined by single-crystal X-ray diffraction analysis. 1 crystallizes in the monoclinic space group P21/n (No. 14) with a = 9.691(2), b = 15.204(2), c = 18.850(2) ? b = 96.44(1), V = 2759.8(7) ?, Z = 4, Mr = 862.08, Dc = 2.075 g/cm3, F(000) = 1680, m (MoKa) = 51.31 cm-1 and T = 296.2 K. With the use of 3667 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.041 and Rw = 0.051. 1 is composed of a distorted Mo2Fe2S4 cubane core with two Br atoms and two h5-C5Me5 groups coordinating at the Fe and Mo sites, respectively. The lengths of MoMo and FeFe bonds are 2.826 and 2.773 ? respectively the mean length of MoFe bond is 2.751 ?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
基金① This work was financially supported by the NNSF of China (No. 29733090 and No. 20173063)Key Project in KIP of CAS (KJCX2-H3) the NNSF of Fujian Province (E0020001)
文摘The title compounds Mo3S4(dtp)3(o-CH3OC6H4COO)(Py) 1 and Mo3S(dtp)3(p-HOC6H4COO)(DMF)稥tOH 2 (dtp = diethyldithiophosphate) were synthesized by thereactions of Mo3S4(dtp)4(CH3CN) and Mo3S4(dtp)3(CH2ClCOO)(Py) with o-methoxylbenzoic acid and p-hydroxybenzoic acid, respectively. Their crystal structures were determined by X-ray diffraction analysis. The crystal data for compound 1: Mo3S10P3C25H42O9N, monoclinic P21/n, Mr = 1201.93, Z = 4, a = 14.164(1), b = 23.065(2), c = 14.732(1) ? = 109.677(1) ? V = 4532(1) ?, D= 1.762 gcm-3, = 1.428 mm-1, F (000) = 2408, R = 0.0739, wR = 0.1528 for 3552 observed reflections (I > 2); and for compound 2: Mo3S10P3C24H48O11N, triclinic P ? Mr = 1227.96, Z = 2, = 10.2098(3), b = 14.3333(4), c = 18.1711(5) ? = 94.694(1), = 102.166(1), = 110.665(1) , V = 2396.5(1)3, Dc = 1.638 gcm-3, = 1.350mm-1, F (000) = 1184, R = 0.0445, wR = 0.1281 for 6597 observed reflections (I > 2). Intermolecular S…S interactions are observed between the molecules of compound 1 while intramolecular O…HC and intermolecular S…HC hydrogen bondings are found in the crystal packing diagram of compound 2.
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This work was supported by the Key Laboratory of Organic Chemistry of Jiangsu Province at Suzhou University.
文摘The reactions of [(h5-C5Me5)Mo(StBu)3] with equimolar FeBr3 in THF afforded a neutral tetranuclear cluster [(h5-C5Me5)2Mo2Fe2S4Br2] 1. The structure of 1 was determined by single-crystal X-ray diffraction analysis. 1 crystallizes in the monoclinic space group P21/n (No. 14) with a = 9.691(2), b = 15.204(2), c = 18.850(2) ? b = 96.44(1), V = 2759.8(7) ?, Z = 4, Mr = 862.08, Dc = 2.075 g/cm3, F(000) = 1680, m (MoKa) = 51.31 cm-1 and T = 296.2 K. With the use of 3667 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.041 and Rw = 0.051. 1 is composed of a distorted Mo2Fe2S4 cubane core with two Br atoms and two h5-C5Me5 groups coordinating at the Fe and Mo sites, respectively. The lengths of MoMo and FeFe bonds are 2.826 and 2.773 ? respectively the mean length of MoFe bond is 2.751 ?
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.
