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1.
Co2(CO)8与4个二硫代双(烷基硫代甲酰胺)类前配体[R2NC(S)S]2反应,得4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物.通过元素分析、IR、1H NMR和MS等方法表征了它们的结构,用X射线衍射法测定了其中一个簇合物Co3(CO)7(μ3-S)[μ,η2-SCN(i-Pr)2](Ⅲ)的晶体结构.晶体属单斜晶系,P21/n空间群,晶胞参数a=1.145 2(2)nm,b=1.502 8(3)nm,c=1.2144(2)nm,a=90°,β=92.15(3)°,γ=90°,V=2.088 5(7)nm3,Z=4,F(000)=1 096,Dc=1.747 mg·m-3,GOF(F2)=0.835,μ=2.588 nm-1.最终因子R[I>2σ(I)]=0.040 7,Rw=0.062 4. 相似文献
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The complexes Pt(nb)3-n(P-iPr3)n (n=1, 2, nb=bicyclo[2.2.1]hept-2-ene), prepared in situ from Pt(nb)3, are useful reagents for addition of Pt(P-iPr3)n fragments to saturated triruthenium clusters. The complexes Ru3Pt(CO)11(P-iPr3)2 (1), Ru3Pt(-H)(3-3-MeCCHCMe)(CO)9(P-iPr3) (2), Ru3Pt(3-2-PhCCPh)(CO)10(P-iPr3) (3), Ru3Pt(-H)(4-N)(CO)10(P-iPr3) (4) and Ru3Pt(-H)(4-2-NO)(CO)10(P-iPr3) (5) have been prepared in this fashion. All complexes have been characterized spectroscopically and by single crystal X-ray determinations. Clusters 1–3 all have 60 cluster valence electrons (CVE) but exhibit differing metal skeletal geometries. Cluster 1 exhibits a planar-rhomboidal metal skeleton with 5 metal–metal bonds and with minor disorder in the metal atoms. Cluster 2 has a distorted tetrahedral metal arrangement, while cluster 3 has a butterfly framework (butterfly angle=118.93(2)°). Clusters 4 and 5 posseses 62 CVE and spiked triangular metal frameworks. Cluster 4 contains a 4-nitrido ligand, while cluster 5 has a highly unusual 4-2-nitrosyl ligand with a very long nitrosyl N–O distance of 1.366(5) Å. 相似文献
8.
本文合成了数个以有机磷作桥基配位体的同核钴和异核铁钴原子簇羰基化合物.通过元素分析、IR谱和~1H-NMR谱测定,确定三核钴簇合物Co_5(CO)_9-(μ_3-PR)和异核铁钴簇合物Co_2Fe(CO)_9(μ_3-PR)的分子骨架Co_3P和Co_2FeP具有三角锥构型,而四核钴簇合物Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2的分子骨架Co_4P_2为八面体构型. 相似文献
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The trinuclear osmium carbonyl cluster, [Os3(CO)10(MeCN)2], is allowed to react with 1 equiv. of [IrCp1Cl2]2 (Cp1 = pentamethylcyclopentadiene) in refluxing dichloromethane to give two new osmium–iridium mixed-metal clusters, [Os3Ir2(Cp1)2(μ-OH)(μ-CO)2(CO)8Cl] (1) and [Os3IrCp1(μ-OH)(CO)10Cl] (2), in moderate yields. In the presence of a pyridyl ligand, [C5H3N(NH2)Br], however, the products isolated are different. Two osmium–iridium clusters with different coordination modes of the pyridyl ligand are afforded, [Os3IrCp1(μ-H)(μ-Cl)(η3,μ3-C5H2N(NH2)Br)(CO)9] (3) and [Os3IrCp1(μ-Cl)2 (η2,μ3-C5H3N(NH)Br)(CO)7] (4). All of the new compounds are characterized by conventional spectroscopic methods, and their structures are determined by single-crystal X-ray diffraction analysis. 相似文献
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Pradeep Mathur Rajiv Trivedi P. Sekar Debojit Chakrabarty Md. Munkir. Hossain Vedavati G. Puranik 《Journal of Cluster Science》1996,7(2):191-198
The new clusters Fe2
M(CO)10(µ3-S)(µ3-Te), I (M=W) and 2 (M=Mo) have been isolated from the room temperature reaction of Fe2(CO)6(µ-STe) andM(CO)5(THF) (M=W, Mo), respectively. Compounds1 and2 have been characterized by IR, 125 Te NMR spectroscopy, and elemental analysis. The structure of compound1 has been established by X-ray crystallography. It belongs to the triclinic space groupP
witha=6.844(2) Å,b=9.397(2) Å,c=13.681(10) Å, =81.64(2)°,=81360r,=812(2)°,V=861.2(3) Å3,Z=2,D
e
=2.835 g cm–3. Full-matrix least-squares refinement of1 converged to R=0.043, andR
w
.=0.115. The structure consists of a Fe2 WSTe square pyramid and the W atom occupies the apical site of the square pyramid. 相似文献
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N. V. Podberezskaya V. A. Maksakov I. V. Slovokhotova S. P. Babailov A. V. Virovets V. P. Kirin 《Journal of Structural Chemistry》1999,40(6):914-925
The reaction of (μ-H)Os3μ-O2CC5H4Mn(CO)3(CO)10 with PPh3 in the presence of Me3NO gave mono- and disubstituted heterometallic complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)(CO)9 and (μ-H)Os3μ-O2CC5H4Mn(CO)3 (PPh3)2(CO)8. Crystal structure determination was performed for three isomeric cluster complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)2(CO)8, which are both geometrical and conformational isomers differing in color. The geometrical isomerism is due to the attachment
of the PPh3 group at different vertices of the Os3 triangle relative to the O2CC5H4Mn(CO)3 bridging ligand. The conform ational isomerism implies that the molecules have the same arrangement of ligands and differ
only in the values of bond angles between the planar fragments of the clusters. 相似文献
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Carlo Allasia Mario Castiglioni Roberto Giordano Enrico Sappa Francesco Verre 《Journal of Cluster Science》2000,11(4):493-509
The title complexes were tested in the hydrogenation of hex-3-yne and of 1,3- and 1,4-cyclohexadiene (CHD) under solid–gas conditions. The clusters were deposited on three “standard” supports, that is, pyrex glass, alumina, and silica. All the clusters, particularly (μ-H)Ru3(CO)10(PPh2), show hydrogenation activity. However, they are not particularly selective toward the formation of monoenes; “disproportionation” of 1,3- and 1,4-CHD to hydrogenated products and benzene also occurs. The hydrogenation activity of the clusters is dependent on their nature, the type of substrate, and the characteristics of the supporting material; silica and pyrex glass are usually more active than alumina. Attempts at detecting the formation of organometallic intermediates or by-products (through IR spectroscopy) were made. HRTEM was used to check for eventual decomposition on some supports. 相似文献
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Xu Feng Chen Yong-Mei Yang Shi-Yan Sun Wen-Hua Yu Kai-Bei 《Transition Metal Chemistry》2000,25(1):108-111
CpMoFeCo(CO)7(3-S) reacts with Cp*M(CO)3Cl or CpM(CO)3Cl (M=W, Mo) to gave the mixed-metal clusters Cp*WCpMoFe(CO)7(3-S) (1), Cp*MoCpMoFe(CO)7(3-S) (2), CpWCp*MoFe(CO)7(3-S) (3), CpMoCp*MoFe(CO)7(3-S) (4) and Cp*WCp*MoFe(CO)7(3-S) (5). The title clusters have been characterized by i.r., 1H/13C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit. 相似文献
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The electron distributions and bonding in Ru3(CO)9(
3-
2,
2,
2-C6H6) and Ru3(CO)9(
3-
2,
2,
2-C60) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru3(CO)9 inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C60 are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–Cfullerene bond lengths are shorter than the corresponding Ru–Cbenzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru3(CO)9(
3-
2,
2,
2-C60) than for Ru3(CO)9(
3-
2,
2,
2-C6H6). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–Cfullerene than Ru–Cbenzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C60 and C6H6. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C60 than to C6H6, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C6H6 permits a greater degree of electron flow and stronger bonding between the Ru3(CO)9 and C60 fragments. Of significance to the reduction chemistry of M3(CO)9(
3-
2,
2,
2-C60) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C60 portion of the molecule. The localized C60 character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C60. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C60. 相似文献
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《Journal of organometallic chemistry》1992,429(3):C41-C45
The compound [Ru4(μ-Se)2(CO)8(μ3-CO)3] (1), has been obtained in good yield by vacuum pyrolysis of [RU3(CO)12] with [Ph2Se2] at 185°C. Reaction of 1 with 1,3-bis(diphenylphosphino)propane at room temperature affords the novel cluster [RU3(μ3-Se)2(CO)7(Ph2P(CH2)3PPh2)] (2). The structures of 1 and 2 have been determined by an X-ray diffraction study. 相似文献
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用Co2(CO)8分别与两个杂环配体C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反应.合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1空间群,I的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有C0作为端基配体与三个Co原子成键.I中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件. 相似文献
20.
《Journal of organometallic chemistry》1987,335(2):249-253
Fe3(CO)9(μ2-H)(μ3-S-t-Bu) reacts with amines in aprotic solvents to give salts [Fe3(CO)9(μ3-S-t-Bu)]−[AminH]+ under deprotonation. The association of cluster and amine under formation of a solvated ion pair follows a second order rate law. The isotope effects kH/kD as well as the rate constants are strongly correlated with the steric demand of the individual bases used: The largest rate constants and the largest isotope effects (up to kH/kD = 13) are observed for bases with the least steric hindrance. 相似文献