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1.
Sofia Nikolaou Daniela M. Tomazela Marcos N. Eberlin Henrique E. Toma 《Transition Metal Chemistry》2008,33(8):1059-1065
The polymetallic [Ru3O(CH3COO)6(py)2(BPE)Ru(bpy)2Cl](PF6)2 complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru3O] moiety with a [Ru(bpy)2(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS)
spectrometry. The [Ru3O(CH3COO)6(py)2(BPE)Ru(bpy)2Cl]2+ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic
of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)2(BPE)] charge-transfer bands and to the [Ru3O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and
−1.29 V (vs SHE) assigned to the [Ru3O]−1/0/+1/+2/+3 and to the bpy0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling
through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation. 相似文献
2.
Four new triphenylgermylruthenium carbonyl compounds HRu(CO)4GePh3, 14; Ru(CO)4(GePh3)2, 15; Ru2(CO)8(GePh3)2, 16; and Ru3(CO)9(GePh3)3(μ-H)3, 17 were obtained from the reaction of Ru(CO)5 with Ph3GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)5 and an oxidative addition of the GeH bond of the Ph3GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh3 ligands in the six coordinate complex. Compound 16 contains two Ru(CO)4(GePh3) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh3 ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru3(CO)10(μ-GePh2)2, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh2 ligands bridging two different edges of the cluster and one bridging CO ligand. Ru3(CO)12 was found to react with Ph3GeH at 97 °C to yield three products: 15, and two new compounds Ru3(CO)9(μ-GePh2)3, 19 and Ru2(CO)6(μ-GePh2)2(GePh3)2, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh2 ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh2 ligands and a terminal GePh3 ligand on each metal atom. All compounds were characterized by a combination of IR, 1H NMR, single-crystal X-ray diffraction analyses.
This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions
to the chemistry of metal chalcogenide cluster complexes. 相似文献
3.
J. Goslar M. Wojciechowska M. Pietrowski M. Zieliński 《Research on Chemical Intermediates》2007,33(8):841-851
Electron paramagnetic resonance (EPR) and infrared (IR) spectroscopy were used to study the formation of ruthenium and adsorbed
species appearing on the catalyst upon the adsorption of CO and O2 on 1.37 wt% Ru/MgF2 catalysts derived from Ru3(CO)12. The presence of Ru
x+ sites in spite of a reductive H2 treatment at 673 K was observed by EPR and IR spectroscopy beside metallic Ru0 species. Both IR and EPR results provided clear evidence for the interaction between surface ruthenium and probe molecules.
The IR spectra recorded after admission of CO showed a band at approx. 2000 cm−1, due to linearly adsorbed CO on Ru0/MgF2 and two bands at higher frequencies (approx. 2140 and approx. 2070 cm−1), related to CO on oxidized Ru
n+ species, e.g., to Ru(CO)3 complex with Ru in the 1+ and/or 2+ state of oxidation and Ru(CO)2 with Ru in the 3+ and/or 4+ state of oxidation. A weak anisotropic EPR signal with g
‖ = 2.017 and g
⊥ = 2.003 is due to O
2
−
radicals and a formation of Ru4+-O
2
−
complex is postulated. The Ru3+ appears to oxidize to Ru4+ and the resulting dioxygen anion is coordinated to the ruthenium. The strong, isotropic EPR signal at g
0 = 2.003 detected upon admission of CO is attributed to CO radical anion rather than to any ruthenium carbonyl complexes. 相似文献
4.
The new alkoxysilyl-functionalized alkynes [HC≡CCH2N(H)C(=O)N(H)(CH2)3Si(OEt)3] and [HC≡C(C6H4)–N(H)C(=O)N(H)(CH2)3Si(OEt)3] have been synthesized using literature methods. These have been reacted with Fe3(CO)12, Ru3(CO)12 and Co2(CO)8. With the iron carbonyl only decomposition was observed: with Ru3(CO)12 splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru3(CO)9[HC=N(CH2)3Si(OEt)3], (μ-H)Ru3(CO)9[C–C(C6H4)NH2] and (μ-H)2Ru3(CO)9[HC–CCH3] occurred. Finally, with Co2(CO)8 formation of complexes Co2(CO)6(HC2R) R=(C6H4)NH2, CH2NH(CO)NH(CH2)3Si(OEt)3, (C6H4)NH(CO)NH(CH2)3Si(OEt)3 containing the intact alkynes could be obtained. 相似文献
5.
Danielle M. Chisholm J. Scott McIndoe Gabriella Bodizs Wee Han Ang Rosario Scopelliti Paul J. Dyson 《Journal of Cluster Science》2007,18(1):303-318
Reaction of [Ru6C(CO)16]2− with an excess of AgX (X = Cl, Br or I) affords heteronuclear clusters of formula [{Ru6C(CO)16Ag2X}2]2− in 80% yield, which for X = I and X = Br/Cl were crystallographically characterised. The formation of the cluster was followed
in solution using electrospray ionisation mass spectrometry (ESI-MS), which revealed the presence of a wide range of clusters
with the general formula [{Ru6C(CO)16}
x
Ag
y
X
z
](2x−y+z)− where x = 1 or 2, y = 1, 2, 3 or 4 and z = 0, 1 or 2. The high yield of the product despite the evident complicated solution speciation is attributed to selective
crystallisation of the observed compound driving the equilibrium toward this product. 相似文献
6.
Three new diruthenium compounds, Ru2(L1)4Cl (1), Ru2(L2)4Cl (2) and Ru2(ap)4F (3) were synthesized and characterized, where L1, L2, and ap are 2-(3-methoxyanilino)pyridinate, 2-(3-propoxyanilino)pyridinate, and 2-anilinopyridinate, respectively. Structural study revealed the Ru–Ru bond lengths of 2. 2816(7) Å (1) and 2. 2785(6) Å (3). All three compounds are S = 3/2 molecules. Each of three diruthenium compounds displays two reversible one electron couples, an oxidation and a reduction, and the potential data appear to indicate that the axial fluoro ligand is a much stronger donor than the chloro ligand. 相似文献
7.
Secco Andrea Carniato Fabio Gatti Giorgio Marabello Domenica Sappa Enrico 《Journal of Sol-Gel Science and Technology》2011,58(2):564-571
Abstract
The triruthenium complexes containing alkynols ligands have been reacted with 2(diphenylphosphino)ethyl-triethoxysilane (dpts), obtaining novel chemically stable disubstituted complexes. The same disubstituted Ru complexes above described were also synthesized following another approach based on the reaction from the phosphine substituted complex Ru3(CO)10(dpts)2 and the same alkynols ligands used to obtain the above triruthenium complexes. One of these stable complexes, the HRu3(CO)7[C≡C(Me)2(OH)](dpts)2 compound was grafted on the mesoporous silica SBA-15 and on γ-Al2O3 surface in order to obtain novel hybrid materials to employ in heterogeneous catalysis. The resulting materials have been characterized by multidisciplinary approach based on inductively coupled plasma-mass spectrometry (ICP-MS), FT-IR, XRD, physisorption measurements and DR-UV–Visible spectroscopy. 相似文献8.
S. V. Osintseva N. A. Shtel’tser P. V. Petrovskii A. Z. Kreindlin F. M. Dolgushin 《Russian Chemical Bulletin》2011,60(1):118-123
The complexes Ru2(CO)6(μ-H)(O=C(CH=CHPh)C(H)=CPh) (5), Ru3(CO)8-(O=C(CH=CHPh)C(H)=CPh)2 (6), and Ru3(CO)7(O=C(CH=CPh)C(H)=CPh)-(O=C(CH2-CH2Ph)C(H)=CPh) (7) were obtained in the reaction of Ru3(CO)12 with dibenzylideneacetone PhCH=CHCOCH=CHPh. The structures of complexes 5 and 6 were established by NMR and IR spectroscopy and elemental analysis. The structure of complex 7 was established by X-ray diffraction. The structural and spectroscopic features of the complexes, as well as their possible
formation and interconversion pathways are discussed. 相似文献
9.
Guochang Chen Xiaohui Zhang Cunyue Guo Guoqing Yuan 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(13):2247-2253
Four kinds of mesoporous molecular sieve SBA-15 (SBA-15-HCl, SBA-15-HPMo, SBA-15-HPW, and SBA-15-HSiW) were synthesized by
different methods or materials. Loaded with RhCl3 and Fe(NO3)3, the SBA-15-HPMo supported catalyst performed well in catalyzing direct conversion of syngas to ethanol. 相似文献
10.
Mohammad El-khateeb Khalil J. Asali Ibrahim Jibril Anas Abuseni Helmar Görls Wolfgang Weigand 《Transition Metal Chemistry》2009,34(4):419-424
A controlled substitution reaction of the chlorine atoms of 1,3,5-benzenetricarbonyl trichloride by the organoiron fragment
(CpFe(CO)2S) has been achieved. The complexes CpFe(CO)2SCO-3,5-C6H3(COCl)2 (1), 1,3-[CpFe(CO)2SCO]2-5-C6H3COCl (2) and 1,3,5-[CpFe(CO)2SCO]3C6H3 (3) were prepared from the reaction of (μ-S
x
)[CpFe(CO)2]2 (x = 3, 4) with 1,3,5-C6H3(COCl)3 in a 1:1, 2:1, or 3:1 metal to ligand molar ratio. The reactions of (1) with amines, thiols, and carboxylic acids produce the trifunctional mono-iron complexes CpFe(CO)2SCO-3,5-C6H3(COY)2 [Y = NR2 (4), SR (5), OCOR (4)]. The X-ray structure determination of (1) is reported. 相似文献
11.
S. P. Gubin L. G. Kuz'mina A. V. Churakov J. A. K. Howard L. A. Polyakova N. A. Kataeva I. F. Golovaneva A. P. Klyagina 《Russian Chemical Bulletin》2005,54(8):1813-1818
The reaction of the carbidocarbonyl cluster [Fe6C(CO)16]2− with ruthenium(IV) hydroxochloride Ru(OH)Cl3 was studied. At 90–100 °C, the reaction gave products of replacement of Fe atoms by Ru in the [Fe6C(CO)16]2− cluster along with degradation products. Treatment of the replacement products with FeCl3 afforded the [Fe2.96Ru3.04C(CO)17] compound (1), which was characterized by X-ray diffraction analysis. The crystals of cluster 1 are composed of two types of octahedral molecules (1a and 1b) in a ratio of 2 : 1. Molecules 1a are in general positions, and molecules 1b are located on twofold axes. In both molecules, the Fe and Ru atoms are disordered over four of six positions.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1761–1766, August, 2005. 相似文献
12.
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) and [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] The reaction of [Ru2(μ‐CO)(CO)5(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 2 ) with dppm yields the dinuclear species [Ru2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 3 ) (dppm = Ph2PCH2PPh2). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru3(CO)12], an excess of tBu2PH and stoichiometric amounts of dppm via the formation of [Ru2(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)2] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses. 相似文献
13.
Trino Suárez Bernardo Fontal María F. Parra Marisela Reyes Fernando Bellandi Juan C. Díaz Pedro Cancines Yuraima Fonseca 《Transition Metal Chemistry》2010,35(3):293-295
Mer-[Mo(CO)3(p-C5H4N-CN)3] was prepared by UV-irradiation of a THF solution of Mo(CO)6 and para-cyanopyridine under heating. The complex was characterized by FT-IR, MS, 1H and 13C NMR and showed catalytic activity for olefin hydroformylation (1-hexene, cyclohexene and 2,3-dimethyl-2-butene as model
olefins; 600 psi synthesis gas (pCO/pH2 = 1); 100 °C; 24 h; toluene). An examination of the complex catalyzed hydroformylation of a real naphtha cut (El Palito refinery,
Venezuela), under the same conditions, also showed activity in the conversion to oxygenated products. 相似文献
14.
Hukkamäki J Suvanto S Suvanto M Pakkanen TT 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):10288-10295
Mesoporous high surface area MCM-41 and SBA-15 type silica materials with fibrous morphology were synthesized and used as support materials for the ALCVD (atomic layer chemical vapor deposition) preparation of Co/MCM-41 and Co/SBA-15 catalysts. Co/MCM-41 and Co/SBA-15 catalysts were prepared by deposition of Co2(CO)8 from the gas phase onto the surfaces of preheated support materials in a fluidized bed reactor. For both silica materials, two different kinds of preparation methods, direct deposition and a pulse deposition method, were used. Pure silica supports as well as supported cobalt catalysts were characterized by various spectroscopic (IR) and analytical (X-ray diffraction, Brunauer-Emmett-Teller, elemental analysis) methods. MCM-41 and SBA-15 fibers showed considerable ability to adsorb Co2(CO)8 from the gas phase. For MCM-41 and SBA-15 silicas, cobalt loadings of 13.7 and 12.1 wt % were obtained using the direct deposition method. The cobalt loadings increased to 23.0 and 20.7 wt % for MCM-41 and SBA-15 silicas, respectively, when the pulse deposition method was used. The reduction behavior of silica-supported cobalt catalysts was found to depend on the catalyst preparation method and on the mesoporous structure of the support material. Almost identical reduction properties of SBA-15-supported catalysts prepared by different deposition methods are explained by the structural properties of the mesoporous support and, in particular, by the chemical structure of the inner surfaces and walls of the mesopores. Pulse O2/H2 chemisorption experiments showed catalytically promising redox properties and surface stability of the prepared MCM-41- and SBA-15-supported cobalt catalysts. 相似文献
15.
New N,N′-dimethylbenzamidine ligands bearing para-Br (HDMBA-Br) and para-I (HDMBA-I) substituents were prepared and crystallographically characterized. The ligand exchange reaction between Ru2(OAc)4Cl and HDMBA-X (X = Br and I) afforded the new Ru2(III) compounds, namely Ru2(DMBA-X)4Cl2, in excellent yields. These new compounds were also characterized with cyclic voltammetric and single crystal X-ray diffraction
techniques.
Dedicated to the memory of Professor F. A. Cotton. 相似文献
16.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(12):2657-2662
Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] and [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)] [Ru3(CO)6(μ‐H)2(μ‐PCy2)2(μ‐dppm)] ( 1 ) (dppm = Ph2PCH2PPh2) reacts under mild conditions with CS2 and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐dppm){μ‐η2‐PCy2C(S)}(μ3‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) Å3. The reaction of [Ru3(CO)7(μ‐H)(μ‐PtBu2)(μ‐PCy2)2] ( 3 ) with CS2 in refluxing toluene affords the 50 VE‐cluster [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 21/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) Å3. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the 31P‐NMR data as an electron‐rich metal cluster. 相似文献
17.
Homoleptic mononuclear and binuclear ruthenium carbonyls Ru(CO)
n
(n = 3–5) and Ru2(CO)
n
(n = 8,9) have been investigated using density functional theory. Sixteen isomers are obtained. For Ru(CO)5, the lowest-energy structure is the singlet D
3h
trigonal bipyramid. Similar to Os(CO)5, the distorted square pyramid isomer with C
2v
symmetry lies ∼7 kJ·mol−1 higher in energy. For the unsaturated mononuclear ruthenium carbonyls Ru(CO)4 and Ru(CO)3, a singlet structure with C
2v
symmetry and a C
s
bent T-shaped structure are the lowest-energy structures, respectively. The global minimum for the Ru2(CO)9 is a singly bridged (CO)4Ru(μ-CO)Ru(CO)4 structure. A triply bridged Ru2(CO)6(μ-CO)3 structure analogous to the known Fe2(CO)9 structure is predicted to lie very close in energy to the global minimum. For Ru2(CO)8, the doubly bridged C
2 structure is predicted to be the global minimum. For the lowest-energy structures of M2(CO)
n
(M = Fe, Ru, Os, n = 9,8), it is found that both iron and ruthenium are favored to form structures containing more bridging carbonyl groups,
while osmium prefers to have structures with less bridging carbonyl groups. The study of dissociation energy shows that the
dissociation of Ru2(CO)9 into the mononuclear fragments Ru(CO)5 + Ru(CO)4 is a less energetically demanding process than the dissociation of one carbonyl group from Ru2(CO)9 to give Ru2(CO)8. 相似文献
18.
Jiaoyun Xia Shu Long Junfeng Yu Yongxian Wang Zhong Cao 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(3):493-499
The purpose of this work was to indirect label IgG with fac-[188Re(CO)3(H2O)3]+ and to check the radiochemical behavior of the labeled product. The compound of (bis(2-pyridylmethyl)-amino)-acetic acid
(L2H) was synthesized and labeled with fac-[188Re(CO)3(H2O)3]+. The labeling yield of 188Re(CO)3–L2H was more than 90%. The effects of protein concentration, reaction time, pH and reaction temperature of labeling of IgG with
188Re(CO)3–L2H were investigated. The conjugation conditions were optimized. The labeled product was analyzed by size exclusion HPLC and
TLC. The stability of 188Re(CO)3–L2H–IgG in vitro was high. The results of this study may be useful for [188Re(CO)3(H2O)3]+ labeling of protein for radioimmunotherapy. 相似文献
19.
《Journal of organometallic chemistry》2006,691(1-2):79-85
Trans-[RuCl2(CO)2(PEt3)2] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt3)(S2X)2] (X = CNMe2, CNEt2, COEt, P(OEt)2, PPh2). Two intermediates have been isolated; trans-[Ru(PEt3)2Cl(CO){S2P(OEt)2}] and trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-S2COEt)], allowing a simple reaction scheme to be postulated involving three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine. Thermolysis of cis-[Ru(CO)(PEt3)(S2CNMe2)2] with Ru3(CO)12 in xylene affords trinuclear [Ru3(μ3-S)2(PEt3)(CO)8] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt3)(S2X)2] (X = NMe2, COEt), trans-[Ru(PEt3)2Cl(CO){S2P(OEt)2}], trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-S2COEt)] and [Ru3(μ3-S)2(PEt3)(CO)8] are reported. 相似文献
20.
Siti Syaida Sirat Imthyaz Ahmed Khan Omar Bin Shawkataly Mohd Mustaqim Rosli 《无机化学与普通化学杂志》2014,640(10):2019-2024
The reaction of Ru3(CO)10(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh3, P(C6H4Cl‐p)3 and PPh2(C6H4Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru3(CO)9(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, 1H NMR, 13C{1H} NMR and 31P{1H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths. 相似文献