共查询到20条相似文献,搜索用时 906 毫秒
1.
Henkelis JJ Jones LF de Miranda MP Kilner CA Halcrow MA 《Inorganic chemistry》2010,49(23):11127-11132
The reaction of CuX(2) (X(-) ≠ F(-)) salts with 1 equiv of 3-pyridyl-5-tert-butylpyrazole (HL) in basic methanol yields blue solids, from which disk complexes of the type [Cu(7)(μ(3)-OH)(4)(μ-OR)(2)(μ-L)(6)](2+) and/or the cubane [Cu(4)(μ(3)-OH)(4)(HL)(4)](4+) can be isolated by recrystallization under the appropriate conditions. Two of the disk complexes have been prepared in crystalline form: [Cu(7)(μ(3)-OH)(4)(μ-OCH(2)CF(3))(2)(μ-L)(6)][BF(4)](2) (2) and [Cu(7)(μ(3)-OH)(4)(μ-OCH(3))(2)(μ-L)(6)]Cl(2)·xCH(2)Cl(2) (3·xCH(2)Cl(2)). The molecular structures of both compounds as solvated crystals can be described as [Cu?Cu(6)(μ-OH)(4)(μ-OR)(2)(μ-L)(6)](2+) (R = CH(2)CF(3) or CH(3)) adducts. The [Cu(6)(μ-OH)(4)(μ-OR)(2)(μ-L)(6)] ring is constructed of six square-pyramidal Cu ions, linked by 1,2-pyrazolido bridges from the L(-) ligands and by basal, apical-bridging hydroxy or alkoxy groups, while the central Cu ion is bound to the four metallamacrocyclic hydroxy donors in a near-regular square-planar geometry. The L(-) ligands project above and below the metal ion core, forming two bowl-shaped cavities that are fully (R = CH(2)CF(3)) or partially (R = CH(3)) occupied by the alkoxy R substituents. Variable-temperature magnetic susceptibility measurements on 2 demonstrated antiferromagnetic interactions between the Cu ions, yielding a spin-frustrated S = (1)/(2) magnetic ground state that is fully populated below around 15 K. Electrospray ionization mass spectrometry, UV/vis/near-IR, and electron paramagnetic resonance measurements imply that the heptacopper(II) disk motif is robust in organic solvents. 相似文献
2.
Michael I. Bruce Michael Schulz Brian W. Skelton Allan H. White 《Journal of Cluster Science》2000,11(1):79-86
Addition of aqueous HCl to Ru5(
3-C=CH2)(-SMe)2(-PPh2)2(CO)10 afforded the structurally characterized carbyne complex Ru5(
3-SMe)(
3-CMe)(-Cl)(-SMe)(-PPh2)2(CO)9, formed by addition of H to the vinylidene ligand; a Cl atom bridges an Ru–Ru bond. 相似文献
3.
<正> C20H40Mo3NO8P3S10, Mr=1123.93, triclinic, P1,a=12.972(3), b=13.763(2), c= 14.515(7)A,α=66.22(3),β=101.72(3),γ=118.90(1)° , V= 2076(2) A3, Z=2,Dc=1.798 g.cm-3, MoKa radiation, final R= 0.040 and Rw=0.056 for 5645 observed reflections. The molecule contains three Mo atoms arranged in a triangle with one capping-S atom, three (μ-S) atoms, one (μ-EtCOO) ligand, one chelate ligand dtp on each Mo atom, and one terminal Py on atom Mo(1). The coordination of Mo atoms is of distorted octahedron. 相似文献
4.
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
5.
《Journal of organometallic chemistry》1995,503(2):C43-C45
Two hexaruthenium carbonyl clusters [Ru6(CO)15(μ-CO)2(μ4-NH) (μ-OMe){μ3-η2-N(H)C(O)OMe}] and [Ru6(CO)16(μ-CO)2-(μ4-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H2Ru3(CO))9NOCH3, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ4-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework. 相似文献
6.
《中国化学快报》1991,(4)
The reaction of Co_2(CO)_8 with EtSPCl_2 gives a new crystal like compound Co_7(μ_7-S)(μ_4-PSEt)(μ-SEt)_2(μ-CO)_2(CO)_(12),whose structure has been determined by single crystal x-ray diffraction.This special com-pound reveals some new features in cluster chemistry~1:The fragmentation of a ligand precursor EtSPCl_2 yieldsthree kinds of fragments,μ_7-S,μ_4-PSEt and μ-SEt,which are ligands in the same cluster molecule.There is anew type of bridging S presented——A μ_7-S atom is interspaced into seven Co core. 相似文献
7.
Yong Qiang MA Xiao CHEN Jing LI* Qing Lan XIE Hong Gen WANG State Key Laboratary of Elemento-Organic Chemistry Nankai University Tianjin Institute of Elemento-Organic Chemistry College of Chemistry Nankai University Tianjin 《中国化学快报》2003,(4)
In recent years the chemistry of mono- or hetero-binuclear complexes containing metal-S(C) bonding modes is a very active field of research. Many useful applications of this kind of complexes have been exploited, such as industrial catalytic hydrodesulfurization (HDS)1,2 and transition metals mediated organic synthesis3-5. In this paper we report that the reduction and subsequent protonation of hetero-binuclear complex [MnRe(CO)6(-S2CPPri3)] occur with cleavage of metal-metal bond and o… 相似文献
8.
The reaction of PtRu5(CO)16(μ6-C),1 with 3-hexyne in the presence of UV irradiation produced two new electron-rich platinum-ruthenium cluster complexes PtRu5(CO)13(μ-EtC2Et)(μ3-EtC2Et)(μ5-C),2 (20% yield) and Pt2Ru6(CO)17(μ-η5-Et4C5)(μ3-EtC2Et) (μ6-C),3 (7% yield). Both compounds were characterized by single-crystal X-ray diffraction analyses. Compound2 contains of a platinum capped square pyramidal cluster of five ruthenium atoms with the carbido ligand located in the center of the square pyramid. A EtC2Et ligand bridges one of the PtRu2 triangles and the Ru-Pt bond between the apical ruthenium atom and the platinum cap. The structure of compound3 consists of an octahedral PtRu5 cluster with an interstitial carbido ligand and a platinum atom capping one of the PtRu2 triangles. There is an additional Ru(CO)2 group extending from the platinum atom in the PtRu5 cluster that contains a metallated tetraethylcyclopentadienyl ligand that bridges to the platinum capping group. There is also a EtC2Et ligand bridging one of the PtRu2 triangular faces to the capping platinum atom. Compounds2 and3 both contain two valence electrons more than the number predicted by conventional electron counting theories, and both also possess unusually long metal-metal bonds that may be related to these anomalous electron configurations. Crystal data for2, space group Pna21,a=19.951(3) Å,b=9.905(2) Å,c=17.180(2) Å,Z=2, 1844 reflections,R=0.036; for3, space group Pna21,α=13.339(1) Å,b=14.671(2) Å,c=11.748(2) Å, α=100.18(1)°, β=95.79(1)°, γ=83.671(9)°,Z=2, 3127 reflections,R=0.026. 相似文献
9.
本文研究由Fe~3(CO)~1~2, PhSeH, Et~3N所形成的配盐[(μ-PhSe)(μ-CO)Fe~2(CO)~6][Et~3NH]与对甲氧基苯甲酰氯、乙酰氯、丙酰氯、苯乙酰氯、α-甲基丙烯酰氯、巴豆酰氯、肉桂酰氯、苯乙炔和β-溴代苯乙烯的反应和机理, 合成了八个既含μ-苯硒又含μ-酰基或μ-烯基配体的六羰基二铁配合物。除用元素分析、MS、IR、^1H NMR表征它们的结构外, 尚测得(μ-PhSe)(μ-σ,π-PhCH=CH)Fe~2(CO)~6的单晶结构。该分子单晶的空间群为P2~1/c, 晶胞参数a=0.9236(2), b=1.0966(3), c=2.0348(6)nm,β=101.53(1)°, D~x=1.77g/cm^3, Z=4, R=0.054, R~w=0.061。 相似文献
10.
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
11.
本文研究由Fe_3(CO)_12,PhSeH,Et_3N所形成的配盐[(μ—PhSe)(μ—CO)Fe_2(CO)_6][Et_3NH]与对甲氧基苯甲酰氯、乙酰氯、丙酰氯、苯乙酰氯、α-甲基丙烯酰氯、巴豆酰氯、肉佳酰氯、苯乙炔和β-溴代苯乙烯的反应和机理,合成八个既含μ-苯硒又含μ-酰基或μ-烯基配体的六羰基二铁配合物除用元素分析,MS、IR、~1H NMR表征它们的结构外,尚测得(μ-PhSe)(μ-σ,π-PhCH=CH)Fe_2(CO)_6的单晶结构.该分子单晶的空间群为P2_1/c,晶胞参数α=0.9236(2),b=1.0966(3),c=2.0348(6)nm,β=101.53(1)°,D_x=1.77g/cm~3、Z=4,R=0.054,R_W=0.061 相似文献
12.
《结构化学》1989,(1)
<正> [Er(u-Met)(u-Gly)(H2O)4]2[Er(u-Met)2(HaO)4]2(ClO4)12(NMet=CH3S-(CH2)2CH(NH2)COOH,Gly=NH2CH2COOH), Mr=3194, trilinic, space group P1, a = 12.375(6),b= 14.041(13), c=19.074(13)A,α=80.85(6),β=80.72(6).γ=62.82(6)° ,Z=1,V= 2896A3,Dc=1.83 g/cm3,R=0.091. The carboxyl groups of Met and Gly in the title complex are bonded to Er atoms as bidentate bridging ligands.There are two different cations located at crystallographic symmetry centers in one unit cell. 相似文献
13.
《结构化学》1992,(2)
<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one. 相似文献
14.
V. V. Tatarchuk A. P. Sergievskaya N. V. Kuratieva I. V. Korol’kov L. A. Sheludyakova S. A. Gromilov 《Journal of Structural Chemistry》2014,55(1):142-146
The crystals of the [Pd3(μ-OH)(μ-CH3COO)5] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) Å3, space group Pna21, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd3(μ-OH)(μ-CH3COO)5], in which the OH? group, together with five CH3COO? anions, is a bridge ligand. 相似文献
15.
《Journal of organometallic chemistry》1996,526(1):145-147
The reaction of [Os3(CO)10(μ-dppm)] (1) with tBu2PH in refluxing diglyme results in the electron-deficient metal cluster complex [Os3(CO)5(μ3-H)(μ-PtBu2)2(μ-dppm)] (2) (dppm = Ph2PCH2PPh2) in good yields. The molecular structure of 2 has been established by a single crystal X-ray structure analysis. In contrast to the known homologue [Ru3(μ-CO)(CO)4(μ3-H)(μ-H)(μ-PtBu2)2(μ-dppm)] (3), no bridging carbonyl ligand was found in 2. The electronically unsaturated cluster 2 does not react with carbon monoxide under elevated pressure, therefore 2 seems to be coordinatively saturated by reason of the high steric demands of the phosphido ligands. 相似文献
16.
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
17.
18.
《Journal of Coordination Chemistry》2012,65(3-4):199-210
Abstract The kinetics for isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 TO Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9, were determined. The overall process involves C[sbnd]H elimination, C[sbnd]S and Ru[sbnd]Ru bond cleavage and Ru2(μ-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH? = 127(3) kJ/mol, ΔS?= 56(11) J/mol-K) and from the pressure dependence (0[sbnd]207 MPa, ΔV? 0 +12.7(1.1) cm3/mol, Δβ? = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metal-metal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C[sbnd]H elimination alone and CO dissociation is not involved. 相似文献
19.
本文报道通过由Fe_3(CO)_(12)/RSH/Et_3N体系所形成的中间物[(μ-CO)(μ-RS)Fe_2(CO)_6]Et_3NH与Ph_2PCl,(p-CH_3C_6H_4)_2PCl或p-CH_3C_6H_4PCl_2反应,合成了7个蝶状Fe_2SP簇合物: (μ-Ph_2P)(μ-RS)·Fe_2(CO)_6(R=Pr~(?),Pr~(?),Bu~(?))、[μ-(p-CH_3C_6H_4)_2P](μ-Pr(?)S)Fe_2(CO)_6以及(μ-p-CH_3C_6H_4PCl)(μ-RS)Fe_2·(CO)_6(R=Et,Pr~(?),Bu~(?))。并对它们的~1H NMR、~(31)P NMR波谱与构象体的关系以及簇合物(μ-Ph_2P)(μ-Bu~(?)S)Fe_2(CO)_6的催化活性进行了初步探讨。 相似文献
20.
Françoise Van Gastel Lisa Agocs Andrew A. Cherkas John F. Corrigan Simon Doherty Ravindranath Ramachandran Nicholas J. Taylor Arthur J. Carty 《Journal of Cluster Science》1991,2(2):131-136
Thecloso octahedral cluster Ru4(CO)11(μ4-PPh)(μ4-S)1 and selenium and tellurium analogues, the first examples of unsaturated ruthenium clusters with a planar metal core and different main group 15 and 16 atoms have been synthesized fromnido Ru4(CO)13(μ3-PPh). An X-ray analysis of1 and Ru4(CO)10(μ4-PPh)(μ4-Se)(PEt3)2a has confirmed thetrans disposition of phosphorus and group 16 main group fragments. 相似文献