Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3...Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3S(C0)7 units linked by a novel phosphido-thio1ato bifunc-tiona1 bridging p'-SPR ligand as backbone.展开更多
Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2（CO）n （n=5 8） are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The ...Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2（CO）n （n=5 8） are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2（CO）＋ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2（CO）6＋ and Pd2（CO）7＋ cations are determined to involve one weakly semibridging CO group. The Pd2（CO）8＋ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a Pd--Pd half bond. The Pd--Pd distance increases with the number of CO ligands.展开更多
The catalytic performance of bimetallic Ru-Co catalysts prepared from a series of H3Ru3Co(CO)12. RuCo2(CO)11 and HRuCo3(CO)12 in CO hydrogenation was investigated, and it was found that the Ru-Co bimetallic carbonyl c...The catalytic performance of bimetallic Ru-Co catalysts prepared from a series of H3Ru3Co(CO)12. RuCo2(CO)11 and HRuCo3(CO)12 in CO hydrogenation was investigated, and it was found that the Ru-Co bimetallic carbonyl cluster-derived catalysts showed a high activity for products, particularly higher oxygenates, compared with the catalysts prepared from impregnation or co-impregnation of monometallic clusters such as [HRu3(CO)11] and Co4(CO)12. The selectivity for oxygenates in CO hydrogenation highly increased with the molar ratio of Co/Ru in the Ru-Co bimetallic cluster to CO/H2 in feed gas. Raising reaction temperature led to an intensive increase of CO conversion and a considerable decrease of selectivity for oxygenates. In situ FT-IR studies revealed that the band at 1584 cm-1 on Ru-Co bimetallic cluster-derived catalysts at 453 K under syngas (CO/H2 = 0. 5) has a good linear relationship to rates of oxygenate formation, which is likely associated with an intermediate to produce oxygenates in CO hydrogenation.展开更多
The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes i...The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623（6）,b = 12.8265（5）,c = 18.2702（7） ,β = 115.95（1）o,V = 3489.9（4） 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296（2） K,C28H18Fe4O14S3,Mr = 898.03,F（000） = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2（CO）6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.展开更多
The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1...The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.展开更多
The title compound (μ PhCH 2Se) 2Fe 2(CO) 6, C 20 H 14 O 6Se 2Fe 2, M r =619.94, is a representative of the family of diselenato bridged hexacarbonyl diiron clusters. It crystallized in the triclinic system, space gr...The title compound (μ PhCH 2Se) 2Fe 2(CO) 6, C 20 H 14 O 6Se 2Fe 2, M r =619.94, is a representative of the family of diselenato bridged hexacarbonyl diiron clusters. It crystallized in the triclinic system, space group P 1(#2), with a=12.973(7), b=12.982(4), c=7.954(4), α=97.74(3)°, β=107.57(4)°, γ=113.65(3)°, V=1118(1) 3, Z=2, D c =1.840 g/cm 3, F(000) =604.00, μ (Mo Kα )=45\^83cm -1 , λ = 0.71069. The structure was refined to R=0.034, R w = 0.045 for 2982 observed reflections ( I> 3.00σ(I )). The molecule exhibits essentially butterfly shaped core Fe 2Se 2 shape with the dihedral angle of 94.13 between two wings. Each methylene in two benzyl groups is attached to the bridged selenato atom by an e type of bond.展开更多
The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)...The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)N(C 6H 5)NC(Me)] and Co 2(CO) 5[μ η 2 P(Fc)N(C 6H 5)NC(Me)].These clusters were characterized by elementary analysis,IR, 1HNMR and MS spectroscopy.During the reaction,the precursor was cleaved in its P=S,P S,P N and C S bonds,respectively,to give the fragments as ligands as listed above that coordinated to Co atoms to form the new cluster molecules.展开更多
By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by ...By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by elemental analysis, IR, 1H NMR and MS spectroscopy.The crystal structure of the cluster has been determined by X-ray single crystal diffraction method.The crystal of the cluster is triclinic, belonging to space group P1 and the cell parameters are as follows: a=8.456 (3), b=11.534(3), c= l1.990(4)A, α=107.36(3), β=108.44(5), γ=90.,18(3)°. Thestructural analysis shows that this molecule contains a tetrahedral cluster framword Co3S and2-thiohydantoin as bridging ligands links up with two cobalt atoms of the framwork by S- andN-atom thus -a five member ring of Co2 NCS has been formed.展开更多
文摘Reaction of dimers of (R) thionophosphine sulfide (R = P - C6H4OMe,SMe ) with Co, (CO), yields the novel hexacobalt cluster [Co'(μ3, -S)2, (CO) 14 (μ4 -μ4- and the trinuclear clusterPSCH,)J 2' In 1, tw0 Co3S(C0)7 units linked by a novel phosphido-thio1ato bifunc-tiona1 bridging p'-SPR ligand as backbone.
文摘Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2（CO）n （n=5 8） are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2（CO）＋ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2（CO）6＋ and Pd2（CO）7＋ cations are determined to involve one weakly semibridging CO group. The Pd2（CO）8＋ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a Pd--Pd half bond. The Pd--Pd distance increases with the number of CO ligands.
文摘The catalytic performance of bimetallic Ru-Co catalysts prepared from a series of H3Ru3Co(CO)12. RuCo2(CO)11 and HRuCo3(CO)12 in CO hydrogenation was investigated, and it was found that the Ru-Co bimetallic carbonyl cluster-derived catalysts showed a high activity for products, particularly higher oxygenates, compared with the catalysts prepared from impregnation or co-impregnation of monometallic clusters such as [HRu3(CO)11] and Co4(CO)12. The selectivity for oxygenates in CO hydrogenation highly increased with the molar ratio of Co/Ru in the Ru-Co bimetallic cluster to CO/H2 in feed gas. Raising reaction temperature led to an intensive increase of CO conversion and a considerable decrease of selectivity for oxygenates. In situ FT-IR studies revealed that the band at 1584 cm-1 on Ru-Co bimetallic cluster-derived catalysts at 453 K under syngas (CO/H2 = 0. 5) has a good linear relationship to rates of oxygenate formation, which is likely associated with an intermediate to produce oxygenates in CO hydrogenation.
基金supported by the Education Department of Jiangxi Province (GJJ11033)
文摘The reaction of [Fe2S2（CO）6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [（μ4-S）{（μ-SCH2（o-OCH3）Ph）Fe2（CO）6}2]（1）.Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623（6）,b = 12.8265（5）,c = 18.2702（7） ,β = 115.95（1）o,V = 3489.9（4） 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296（2） K,C28H18Fe4O14S3,Mr = 898.03,F（000） = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2（CO）6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.
文摘The chiral sulfido cluster (η5-C5H5)WFeCo(CO)8(μ3--S) was synthesized by refluxing a solution of HFe2Co(CO)9 (μ3,--S) and (η5-C5H5)Fe(CO)3Cl in tetrahydrofuran. It was characterized by elemental analysis, IR and 1H/13C--NMR. Theproposal concerning mechanism was discussed herewith and the structure was reportedas well. Crystallographic data: Mr= 563. 85, monoclinicl P21/n(# 14); a= 8. 009(2), b= 17. 600(5), c=12. 003(4) A; β=95. 91(2)°; V= 1683. 0 (9) A3; Z=4;Dc=2. 22 g. cm-3; F(000) = 1048, μ=89. 27 cm-1 ; final R=0. 039 and Rw=0. 049for 2121 observable reflections with (I≥3. cσ(I) ). The crystal structure determinationshows that S atom coordinates to all three metal (W,Fe,Co) atoms in a μ3,-fashion,thetitle cluster core has the tetrahedral skeleton.
文摘The title compound (μ PhCH 2Se) 2Fe 2(CO) 6, C 20 H 14 O 6Se 2Fe 2, M r =619.94, is a representative of the family of diselenato bridged hexacarbonyl diiron clusters. It crystallized in the triclinic system, space group P 1(#2), with a=12.973(7), b=12.982(4), c=7.954(4), α=97.74(3)°, β=107.57(4)°, γ=113.65(3)°, V=1118(1) 3, Z=2, D c =1.840 g/cm 3, F(000) =604.00, μ (Mo Kα )=45\^83cm -1 , λ = 0.71069. The structure was refined to R=0.034, R w = 0.045 for 2982 observed reflections ( I> 3.00σ(I )). The molecule exhibits essentially butterfly shaped core Fe 2Se 2 shape with the dihedral angle of 94.13 between two wings. Each methylene in two benzyl groups is attached to the bridged selenato atom by an e type of bond.
文摘The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)N(C 6H 5)NC(Me)] and Co 2(CO) 5[μ η 2 P(Fc)N(C 6H 5)NC(Me)].These clusters were characterized by elementary analysis,IR, 1HNMR and MS spectroscopy.During the reaction,the precursor was cleaved in its P=S,P S,P N and C S bonds,respectively,to give the fragments as ligands as listed above that coordinated to Co atoms to form the new cluster molecules.
文摘By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by elemental analysis, IR, 1H NMR and MS spectroscopy.The crystal structure of the cluster has been determined by X-ray single crystal diffraction method.The crystal of the cluster is triclinic, belonging to space group P1 and the cell parameters are as follows: a=8.456 (3), b=11.534(3), c= l1.990(4)A, α=107.36(3), β=108.44(5), γ=90.,18(3)°. Thestructural analysis shows that this molecule contains a tetrahedral cluster framword Co3S and2-thiohydantoin as bridging ligands links up with two cobalt atoms of the framwork by S- andN-atom thus -a five member ring of Co2 NCS has been formed.
