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
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
A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-cr...A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.展开更多
Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Com...Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Compound 1 crystallizes in the monoclinic,space group P2_1/n with lattice parameters:a=1.2906(4) nm, b=1.5006(8) nm,c=3.1484(6) nm,β= 92.12(2)°,V=6.093(3) nm 3,Z=4. The structure of the anion of 1 contains an incomplete WS_3Cu_3 cubane-like core in which two CuI units are bridged by a dppm ligand. The W—Cu distances vary in the range of 0.2644(1)—0.2793(1) nm. The optical limiting (OL) properties of 1 in MeCN were measured with the laser pulse-width of 12-ns at 532 nm,and the nanosecond OL effect may be due to the reverse saturable absorption (RSA) related to the excited triplet states.展开更多
The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432....The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432. 95,orthorhombic space group Fdd2, a= 29. 9519 (2), b=13. 4719 (2), c= 25. 8612 (4)A, V= 10435. 2 (4), Z= 8, Dc= 1.824 g/cm3, F(000)= 5616,μ(MoKa) =50.64 cm-1, the final R =0.091 and wR =0. 206 for those 3401 unique reflectionshaving . The crystal structure determination shows that the cluster consists of a tetrahedral VS4 core encapsulated by a distorted octahedral array of six copperatoms which have two different coordination geometries, trigonal and tetrahedral.展开更多
The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57,...The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57, monoclinicspace group C2/c, a= 17. 864(3), b= 25. 946(8), c= 24.071 (7),β= 112. 79(2)°,V = 10285. 9, Z= 4, Dc= 1. 28 g/cm3, F(000) = 4192, μ(MoKa) = 16. 7 cm-1,the final R=0.065 and Rw =0.074 for 4051 unique reflections with I> 3σ(I). Thestructure can be described as a metal-sulfur dodecahedral cage fused by two incompletecubane-like VS3Cu3 units connected by Cu - S bonds. The Cu - S bonds within theasymmetric VS3Cu3 unit are slightly shorter than those linking the two centrosymmetrically related VS3Cu3 units. The six copper and two vanadium atoms display asomewhat distorted cubane array with a μ4-S atom on each face of the metal cubane.展开更多
The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was dete...The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.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
Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char...Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char- acterized by elementary analysis, IR, UV-Vis, 1H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P21/c with a=1.7998(4) nm, b=2.0836(4) nm, c=1.9135(4) nm, β=113.63(3)°, V=6.574(3) nm3, Z=4. The cluster cation [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl]+ of 2 contains a strongly distorted, cubane-like structure [WS3Cu3Cl] in which one Cl weakly fills into the void of the nido-like [WS3Cu3] fragment with three relatively long Cu-Cl distances. CCDC: 270415.展开更多
Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA,...Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm3, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three Cu(4-bpy)+ units are linked by a triply-bridging WOS32- unit and a doubly-bridging iodine atom. CCDC: 266412.展开更多
We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechan...We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation（denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively）： RER1 is COgas ＋ O2（ads） → O（ads） ＋ CO2（gas）; RER2 is COgas ＋ O2（ads） → CO3（ads） → O（ads） ＋ CO2（gas）; RLH1 refers to CO（ads） ＋ O2（ads） → O（ads） ＋ CO2（gas）; RLH2 refers to CO（ads） ＋ O2（ads） → OOCO（ads） → O（ads） ＋ CO2（gas） and RLH3 refers to O2（ads） ＋ CO（ads）→ O（ads） ＋ O（ads） ＋ CO（ads） → O（ads） ＋ CO2（gas）. These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.展开更多
The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. I...The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. Its structure was determined by single-crystal X-ray diffraction analysis, and the crystal data for the compound: triclinic, P , a = 9.7442(2), b = 14.124(3), c = 15.410 (3) ? ?= 98.96(3), ?= 93.82(3), ?= 94.08(3)? V = 2083.7(7) ?3, Z = 2, Dc = 1.66 g/cm3, (MoK? = 1.31mm-1, F(000) = 1052,C30H35N5S10Cu4,Mr = 1040.45. The structure was refined to R = 0.0393 and wR = 0.1158 for 9281 independent reflections. The title crystal consists of a neutral complex molecule [Cu4(S5)2(4-CH3C5H4N)4] and a 4-methylpyridine solvent molecule. In the neutral complex, the four Cu atoms are in a distorted tetrahedral arrangement and the nonbonding Cu…Cu distances in the copper tetrahedron range from 3.1414 to 3.8488 , and the CuS bond lengths vary from 2.2839 to 2.3670 ?展开更多
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the Natural Science Foundation of China Fujian Province and Chinese Academy of Sciences.
文摘A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 2 710 3 6) ,theNaturalScienceFoundationoftheEducationCommitteeofJiangsuProvince (No .0 2KJB15 0 0 0 1) ,StateKeyLabofCoordinationChemistryofNanjingUniversity ,andtheScientificResearchF
文摘Reaction of [PPh_4][(η 5-C_5Me_5)WS_3] with CuI,CuBr and bis^(diphenylphosphino)methane (dppm) (molar ratio=1∶2∶1∶1) in MeCN gave rise to [PPh_4][(η 5-C_5Me_5)WS_3(CuBr)(CuI)_2-(μ-dppm)] (1) in high yield. Compound 1 crystallizes in the monoclinic,space group P2_1/n with lattice parameters:a=1.2906(4) nm, b=1.5006(8) nm,c=3.1484(6) nm,β= 92.12(2)°,V=6.093(3) nm 3,Z=4. The structure of the anion of 1 contains an incomplete WS_3Cu_3 cubane-like core in which two CuI units are bridged by a dppm ligand. The W—Cu distances vary in the range of 0.2644(1)—0.2793(1) nm. The optical limiting (OL) properties of 1 in MeCN were measured with the laser pulse-width of 12-ns at 532 nm,and the nanosecond OL effect may be due to the reverse saturable absorption (RSA) related to the excited triplet states.
文摘The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432. 95,orthorhombic space group Fdd2, a= 29. 9519 (2), b=13. 4719 (2), c= 25. 8612 (4)A, V= 10435. 2 (4), Z= 8, Dc= 1.824 g/cm3, F(000)= 5616,μ(MoKa) =50.64 cm-1, the final R =0.091 and wR =0. 206 for those 3401 unique reflectionshaving . The crystal structure determination shows that the cluster consists of a tetrahedral VS4 core encapsulated by a distorted octahedral array of six copperatoms which have two different coordination geometries, trigonal and tetrahedral.
文摘The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57, monoclinicspace group C2/c, a= 17. 864(3), b= 25. 946(8), c= 24.071 (7),β= 112. 79(2)°,V = 10285. 9, Z= 4, Dc= 1. 28 g/cm3, F(000) = 4192, μ(MoKa) = 16. 7 cm-1,the final R=0.065 and Rw =0.074 for 4051 unique reflections with I> 3σ(I). Thestructure can be described as a metal-sulfur dodecahedral cage fused by two incompletecubane-like VS3Cu3 units connected by Cu - S bonds. The Cu - S bonds within theasymmetric VS3Cu3 unit are slightly shorter than those linking the two centrosymmetrically related VS3Cu3 units. The six copper and two vanadium atoms display asomewhat distorted cubane array with a μ4-S atom on each face of the metal cubane.
基金supported by Suzhou University(XQ109020 and Q4109927)
文摘The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.
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Reaction of a preformed cluster [｛(η5-C5Me5)WS3｝3Cu7(MeCN)9](PF6)4 (1) in MeCN with LiCl and PPh3 gave rise to a tetranuclear cationic cluster [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl](PF6) (2). The title compound 2 was char- acterized by elementary analysis, IR, UV-Vis, 1H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P21/c with a=1.7998(4) nm, b=2.0836(4) nm, c=1.9135(4) nm, β=113.63(3)°, V=6.574(3) nm3, Z=4. The cluster cation [(η5-C5Me5)WS3｛Cu(PPh3)｝3Cl]+ of 2 contains a strongly distorted, cubane-like structure [WS3Cu3Cl] in which one Cl weakly fills into the void of the nido-like [WS3Cu3] fragment with three relatively long Cu-Cl distances. CCDC: 270415.
文摘Reaction of (NH4)2WOS3 with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster WOS3Cu3I(4-bpy)3·0.25EtOH. This compound was characterized by elementary analysis, IR, 1H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm3, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three Cu(4-bpy)+ units are linked by a triply-bridging WOS32- unit and a doubly-bridging iodine atom. CCDC: 266412.
基金supported by the National Natural Science Foundation of China(Nos.51574090 and 21773030)Natural Science Foundation of Fujian Province(2017J01409)
文摘We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation（denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively）： RER1 is COgas ＋ O2（ads） → O（ads） ＋ CO2（gas）; RER2 is COgas ＋ O2（ads） → CO3（ads） → O（ads） ＋ CO2（gas）; RLH1 refers to CO（ads） ＋ O2（ads） → O（ads） ＋ CO2（gas）; RLH2 refers to CO（ads） ＋ O2（ads） → OOCO（ads） → O（ads） ＋ CO2（gas） and RLH3 refers to O2（ads） ＋ CO（ads）→ O（ads） ＋ O（ads） ＋ CO（ads） → O（ads） ＋ CO2（gas）. These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.
基金Supported by the Natural Science Foundation of Fujian Education Committee(JB01045)
文摘The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. Its structure was determined by single-crystal X-ray diffraction analysis, and the crystal data for the compound: triclinic, P , a = 9.7442(2), b = 14.124(3), c = 15.410 (3) ? ?= 98.96(3), ?= 93.82(3), ?= 94.08(3)? V = 2083.7(7) ?3, Z = 2, Dc = 1.66 g/cm3, (MoK? = 1.31mm-1, F(000) = 1052,C30H35N5S10Cu4,Mr = 1040.45. The structure was refined to R = 0.0393 and wR = 0.1158 for 9281 independent reflections. The title crystal consists of a neutral complex molecule [Cu4(S5)2(4-CH3C5H4N)4] and a 4-methylpyridine solvent molecule. In the neutral complex, the four Cu atoms are in a distorted tetrahedral arrangement and the nonbonding Cu…Cu distances in the copper tetrahedron range from 3.1414 to 3.8488 , and the CuS bond lengths vary from 2.2839 to 2.3670 ?
