共查询到20条相似文献,搜索用时 15 毫秒
1.
Giuseppe Fachinetti Tiziana FunaioliPier Francesco Zanazzi 《Journal of organometallic chemistry》1993,460(2):C34-C36
Both [Rh4(CO)12] and [Rh6(CO)16] disproportionate in pyridine to cis-[Rh(CO)2(py)2]+ and [Rh5(CO)13(py)2]−. In the same solvent, cis-[Rh(CO)2(py)2]+ is reduced by CO/H2O to [(py)2H][Rh5(CO)13-(py)2], which has been structurally characterized. 相似文献
2.
L 《Journal of organometallic chemistry》1997,530(1-2):169-176
A series of rhenium complexes [fac-Re(bpy)(CO)3L][SbF6] (bpy = 2,2′-bipyridine, L = P(nBu)3, PEt3, PPh3, P(OMe)Ph2, P(OiPr)3, P(OEt)3, P(OMe)3, P(OPh)3) has been prepared and characterized by the IR, UV-vis, 1H NMR, 31P NMR, X-ray photoelectron spectroscopy and electrochemical techniques. Variations in the electronic properties, i.e. CO stretching, metal-to-ligand charge transfer transition, and 31P NMR chemical shifts were interpreted on the basis of the electron-acceptor strength of L. However, the redox potential corresponding to [Re(bpy)(CO)3L]+/[Re(bpy−)(CO)3L]showed ‘V-character type’ changes after the increase in the electron-acceptor strength of L. Variation of the P(2p) binding energy of the phosphorus atom indicated that the electronic structure of the coordinated phosphorus atom was strongly influenced by the electronic properties of the directly attached substituents. 相似文献
3.
Rolf W. Albach Ulrich Küsthardt Joachim Behm Birgit EbeitMarie-Helne Delville Didier Astruc 《Journal of organometallic chemistry》1993,450(1-2):165-170
Electrochemical one-electron reduction of the dinuclear d1-d1 organorhenium oxides Me4Re2O4 (1) and (c-Pr)4Re2O4 (2) reversibly yields the mono-anions 1− and 2 −. Further electrochemical reduction is irreversible. The observed mechanisms upon electrochemical reduction and the involved electrode kinetics are discussed in the light of the electrochemical data. Chemical reduction by cobaltocene leads quantitatively to the same dinuclear radical complexes 1− and 2−, the EPR spectra of which support the formulation as ReVReVI, mixed-valence dimers. Reoxidation can be achieved with ferricinium hexafluorophosphate. Upon controlled exposure to oxygen the extraordinarily air-sensitive anion 1− forms the unprecedented linear trinuclear rhenium cluster [Cp2Co][Me6Re3O6] (4). The mechanism of this aggregation reaction involving disproportionation is discussed. The crystal and molecular structure of the anion 4 has been determined, the trimeric anion has almost C2v symmetry, and the Re-Re-Re angle is nearly linear (177.83(2)°). 相似文献
4.
The anion [Fe4S3(NO)7]− undergoes slow exchange with labelled nitrite [15NO2]− to yield a product [Fe4S3(14NO)(15NO)6]− in which complete isotopic exchange has occurred at the basal Fe(NO)2 groups, but with no exchange at the apical Fe(NO) group. The neutral Fe4S4(NO)4 reacts rapidly with [15NO2− to give fully exchanged [Fe4S3(15NO)7]−, and it is proposed that the conversion proceeds by fragmentation, followed by complete isotopic exchange and rapid reassembly. The binuclear anion [Fe2S2(NO)4]2− also yields, with [15NO2]2− in CD2Cl2 solution, the fully exchanged [Fe4S3(15NO)7]−, and a mechanism involving successive fragmentation, exchange and reassembly steps is proposed; however in aqueous solution, a clean exchange reaction occurs to give [Fe2S2(15NO)4]2−. Neutral binuclear esters Fe2(SR)2(NO)4 (R = Me, Et, or Ph) with [14NO2]− yield the mononuclear paramagnetic [Fe(14NO)2(14NO2)2]−, and with [15NO2]− the analogous [Fe(15NO)2(15NO2)2]−. 相似文献
5.
The coordinatively unsaturated uranium(IV) complex U[N(C6H5)2]4 has been prepared via the stoichiometric reaction of diphenylamine with [(Me3Si)2N]2
H2. U[N(C6H5)2]4 coordinates Lewis bases such as Et2O, THF, pyridine or (EtO)3PO, based on electronic absorption spectroscopy and 1H NMR studies. Exchange between U[N(C6H5)2]4 and U[N(C6H5)2]4(L), where L is THF or pyridine, is rapid on the NMR time-scale between 307 and 323 K. Measurement of equilibrium constants for L = THF provides ΔH and ΔS values of −60 kJ mol−1 and −1.8 × 102 J K−1 mol−1, respectively. U[N(C6H5)2]4 coordinates and binds (EtO)3PO much more tightly (Keq = & > 104 M−1) than THF or pyridine with the exchange rate between U[N(C6H5)2]4 and U[N(C6H5)2]4[OP(OEt)3] being close to the NMR time-scale. 相似文献
6.
Reactions among Cu(ClO4)2 · 6H2O, Cu(acac)2/VO(acac)2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu2L(acac)(H2O)2]ClO4 (1), [Cu4L2(acac)2(py)2](ClO4)2 (2) and (VO2)2L2Cu2(acac)2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO4− anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1. 相似文献
7.
The compounds [MI2(CO)3(NCMe)2] (M = Mo or W) react with one equivalent of thiourea (tu) in MeOH or N,N,N′,N′-tetramethylthiourea (tmtu) in CH2Cl2 at room temperature to initially afford the monoacetonitrile compounds [MI2(CO)3(NCMe)L] (L = tu or tmtu) which rapidly transform to the isolated iodide bridged dimers, [M(μ-I)I(CO)3L]2 with loss of acetonitrile. Reaction of [WI2(CO)3(NCMe)2] with two equivalents of tu or tmtu gave the expected mononuclear seven-coordinate compounds [WI2(CO)3L2]. However, reaction of [MoI2(CO)3(NCMe)2] with two equivalents of tu or tmtu rapidly affords the iodide-bridged dimers [Mo(μ-I)I(CO)2L2]2 with loss of carbon monoxide from [MoI2(CO)3L2]. The low temperature (−70°C) 13C NMR spectrum of [Mo(μ-I)I(CO)2 {SC(NMe2)2}2]2 suggests the complex is based on two capped octahedra with a carbonyl ligand capping each octahedral face. 相似文献
8.
Anthony R. Butler Christopher Glidewell Ian L. Johnson John C. Walton 《Polyhedron》1987,6(12):2085-2090
The tetrathiomolybdate ion [MoS4]2− reacts in DMF solution with Roussin esters Fe2(SR)2(NO)4 (R = Me, Et, n-Pr, i-Pr, n-Bu,t-Bu, n-C5H11) to yield the paramagnetic iron nitrosyls [Fe(NO)2(SR)2]− (1), [Fe(NO)2(S2MoS2]− (2) and [Fe(NO)(S2MOS2)2]− (3). The new complexes (2) and (3) have been characterized by EPR spectroscopy and the assignment to them of constitutions based respectively upon tetrahedral and square pyramidal iron is supported by EHMO calculations. Fe2(SPh)2(NO)4 with [MoS4]2− yields only [Fe(NO)2(SPh)2]−, and preformed (3) reacts with PhS− to give firstly EPR-silent species, and then [Fe(NO)2(SPh)2]−. The mononitrosyl (3) can also be formed by reaction of [MoS4]2− with [Fe4S3(NO)7]−, Fe4S4(NO)4, or Fe2I2(NO)4. 相似文献
9.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η5---C5Me4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η5---C5Me4Et)(CO)X}2{Ph2P(CH2)nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η5---C5Me4Et)(CO)2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η5---C5Me4Et)(CO)L]+Cl− (L = phen or (NH2CH2CH2)2NH). Reaction of Ru(η5---C5Me4Et)(CO)2Br with AgOAc yielded the corresponding acetato complex Ru(η5---C5Me4Et)(CO)20Ac. Ru(η5--- C5Me4Et)(CO)2X reacts with AgY (Y = BF4 or PF6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η5---C5Me4Et)(CO)2(solvent)]+Y−, which readily react with ligands L to yield ionic derivatives of the type [Ru(η5---C5Me4Et)(CO)2L]+Y− (where L = CO, NCMe, py, C2H4 or MeO2CCCCO2Me). 相似文献
10.
The oxidation of Cp2MCl2 (M= Mo, W) with perfluortriazinium tetrafluoroborate, [(FCN)3F]+[BF4]−, in the presence of a flouride ion acceptor (BF3 or PF5) in SO2 solution yielded the cationic metallocene complexes [Cp2MCl 2]2+[BF4]− or [Cp2MCl2] 2+[BF4]−[PF6]− (M = Mo, W), respectively. In these reactions, for the first time the perfluortriazinium cation has proved to be easy to handle and a useful oxidizer in organometallic chemistry. The oxidizer strength of three fluorotriazinium cations, [(XCN)3F]+ (X = F, Cl, H), has been computed ab initio (HF/6 − 31 + G) and calibrated on literature data which were obtained by local density functional calculations. It was anchored to its F+ zero point by an experimental value for KrF+. ab]Die Oxidation von Cp2MCl2 mit (M = MO, W) Perfluortriaziniumtetrafluoroborat, [(FCN)3F]+[BF4]−, in Anwesenheit eines Fluoridionenakzeptors (BF3 oder PF5) führte in SO2-Lösung zur Bildung der kationischen Metallocen-Komplexe [Cp2MCl2+]2+[BF4]2− bzw. [Cp2MCl2]2+[BF4]− [PF6]− (M = Mo, W). In diesen Reaktionen konnte erstmals gezeigt werden, daß Perfluortriazinium-Kationen einfach zu handhabende und nützliche Oxidationsmittel im Bereich der metallorganischen Synthese darstellen. Das (Mdationsvermögen von drei Fluorotriazinium-Kationen, [(XCN)3F]+(X = F, Cl, H), wurde ab initio berechnet (HF/6 − 31 + G) und mit Hilfe von Literaturdaten, die mittels local density functional-Berechnungen erhalten und am experimentellen Wert von KrF + bezüglich des F+ Nullpunktes verankert wurden, kalibriert. 相似文献
11.
Synthesis of solid [Cr(nta)(H2O)2] 1, kinetics and equilibrium of ots reaction with pentane-2,4-dione (Hpd) to form [Cr(nta)(pd)]− 2 (H3nta is nitrilotriacetic acid), aquation of 2 into 1, and some related reactions have been described. Parallel proton-independent and inverse proton-dependent paths lead from 1 to 2. The [H+]−1 path arises from metal assisted deprotonation of HE, the enol form of Hpd. Aquation of 2 into 1 involves [Cr(Hnta)(pd)(H2O]+ 2H (Hnta is tridentate nta) in addition to 2. The nta comples 1 is considerably more labile and a weaker acid than [Cr(H2O)6]3+. 相似文献
12.
Brian K. Nicholson 《Journal of organometallic chemistry》1992,440(3):411-418
The specific additions of one, three or four Ph3PAu groups to [M(CO)5]− (M=Mn, Re) are described. Thus [M(CO)5] − in THF reacts with [(Ph3PAu)3O]BF4 to give [(Ph3PAu)4Mn(CO)4]BF4. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au4Mn core with the Mn in an equatorial site. The previously known neutral (Ph3PAu)3M(CO)4 clusters are formed by addition of two Ph3PAu groups, using the mixed reagent [(Ph3PAu) 3O]BF4/[ppn][Co(CO)4], to Ph3PAuM(CO)5, which itself is readily prepared from [M(CO)5]− and Ph3PAuCl. 相似文献
13.
The bis(μ3-ethylidyne) tricobalt cluster [(CpCo)3(μ3-CCH3)2] (1b) is protonated by trifluoroacetic acid to give the dicobalt edge-protonated cation [H(CpCo)3(μ3-CCH3)2]+ [lb + H]+. Protonation of the μ3-ethylidyne tetracobalt cluster hydride [H(CpCo)4(μ3-CCH3)] (3) takes place in two consecutive steps. At low temperature [H2(CpCo)4(μ3-CCH3)]+ [3 + H]+ is formed first, and is then slowly converted into [H3(CpCo)4(μ3-CCH3)]2+ [3 + 2H]2+ by an excess of acid. As judged by the 1H NMR data and the crystal structure of [3 + X]+[(CF3COO)2X]− (X = H or D) the endo hydrogens in [3 + H]+ and [3 + 2H]2+ occupy μ3-(Co3) face capping hydridic positions. The cations [1b + H]+ and [3 + H]+ show hydride fluxionality in solution, which in the case of [3 + H]+ can be frozen out on the NMR timescale at low temperature (ΔG ≠ (203 K) = 40.8 kJ/mol). The structure of [3 + X]+ [(CF3COO)2X]− (X = H or D) was determined by X-ray crystallography. One of the hydrides/deuterides is located on the crystallographic mirror plane, capping a tricobalt face of the cluster cation. The other endo hydrogen atom is believed to be disordered between the other two μ3-(Co3) sites, which are related by space group symmetry. Deuteronation of 3 shows a strong normal kinetic deuterium isotope effect. From the temperature independence of the 1H NMR spectrum of [3 + 2D]2+ a non-fluxional solution structure can be inferred. In all the systems studied, hydridic (μ2- or μ3-) sites are thermodynamically preferred to possible isomeric agostic CoHC or Co2HC sites for the endo hydrogens. Agostic interactions cannot, however, be ruled out in transient intermediates during the course of the protonations. 相似文献
14.
Alison J. Downard Brian H. Robinson Jim Simpson 《Journal of organometallic chemistry》1987,320(3):363-384
The generality of a two-electron reduction process involving an
mechanism has been established for M3(CO)12 and M3(CO)12−n(PPh3)n (M = Ru, Os) clusters in all solvents. Detailed coulometric and spectral studies in CH2Cl2 provide strong evidence for the formation of an ‘opened’ M3(CO)122− species the triangulo radical anions M3(CO)12−· having a half-life of < 10−6 s in CH2Cl2. However, the electrochemical response is sensitive to the presence of water and is concentration dependent. An electrochemical response for “opened” M3(CO)122− is only detected at low concentrations < 5 × 10−4 mol dm−3 and under drybox conditions. The electroactive species ground at higher concentrations and in the presence of water M3(CO)112− and M6(CO)182− were confirmed by a study of the electrochemistry of these anions in CH2Cl2; HM3(CO)11− is not a product. The couple [M6(CO)18]−/2− is chemically reversible under certain conditions but oxidation of HM3(CO)11− is chemically irreversible. Different electrochemical behaviour for Ru3(CO)12 is found when [PPN][X] (X = OAc−, Cl−) salts are supporting electrolytes. In these solutions formation of the ultimate electroactive species [μ-C(O)XRu3(CO)10]− at the electrode is stopped under CO or at low temperatures but Ru3(CO)12−· is still trapped by reversible attack by X presumably as [η1-C(O)XRu3(CO)11]−. It is shown that electrode-initiated electron catalysed substitution of M3(CO)12 only takes place on the electrochemical timescale when M = Ru, but it is slow, inefficient and non-selective, whereas BPK-initiated nucleophilic substitution of Ru3(CO)12 is only specific and fast in ether solvents particulary THF. Metal---metal bond cleavage is the most important influence on the rate and specificity of catalytic substitution by electron or [PPN]-initiation. The redox chemistry of M3(CO)12 clusters (M = Fe, Ru, Os) is a consequence of the relative rates of metal---metal bond dissociation, metal-metal bond strength and ligand dissociation and in many aspects resembles their photochemistry. 相似文献
15.
María P. García M. Victoria Jimnez Teresa Luengo Luis A. Oro 《Journal of organometallic chemistry》1996,510(1-2):189-195
The reaction of the anionic mononuclear rhodium complex [Rh(C6F5)3Cl(Hpz)]t- (Hpz = pyrazole, C3H4N2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds [(C6F5)3Rh(μ-Cl)(μ-pz)M(L2)] [M = Rh, L2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO)2 (4); M = Ir, L2 = COD (3)]. The complex [Rh(C6F5)3(Hbim)]− (5) has been prepared by treating [Rh(C6F5)3(acac)]− with H2bim (acac = acetylacetonate; H2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes [(C6F5)3Rh(μ-bim)M(L2)]− [M = Rh, L2 = COD (6) or TFB (7); M = Ir, L2 = COD (8); M = Pd, L2 = η3-C3H5 (9)]. With [Rh(acac)(CO)2], complex 5 yields the tetranuclear complex [{(C6F5)3Rh(μ-bim)Rh(CO)2}2]2−. Homodinuclear RhIII derivatives [{Rh(C6F5)3}2(μ-L)2]·- [L2 = OH, pz (11); OH, StBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion [{Rh(C6F5)3(μ-OH)}2]2− by the corresponding ligands. The reaction of [Rh(C6F5)3(Et2O)x] with [PdX2(COD)] produces neutral heterodinuclear compounds [(C6F5)3Rh(μ-X)2Pd(COD)] [X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh3+) salts. 相似文献
16.
Alberto R. Dias Adelino Galvo M. Helena Garcia Maria J. Villa de Brito 《Journal of organometallic chemistry》2001,620(1-2):276-281
An unexpected trimanganese(I) tetrathiolate-bridged complex, [Mn3(CO)9(μ-SC6H5)4]−, with an incomplete cubane structure, was obtained by thermal reaction of [Mn2(CO)10] with [Mo(η5-C5H5)2(SC6H5)2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η5-C5H5)2(H)CO]+, directed towards the vacant site of the cubane structure. Possible routes by which the anion and the cation could be formed are discussed. 相似文献
17.
Kom-Bei Shiu Shin-Jay Yu Yu Wang Gene-Hsiang Lee 《Journal of organometallic chemistry》2002,650(1-2):37-42
Treatment of [Ru2(CO)4(MeCN)6][BF4]2 or [Ru2(CO)4(μ-O2CMe)2(MeCN)2] with uni-negative 1,1-dithiolate anions via potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium tert-butylthioxanthate, and ammonium O,O′-diethylthiophosphate gives both monomeric and dimeric products of cis-[Ru(CO)2(η2-(SS))2] ((SS)−=Me2NCS2− (1), Et2NCS2− (2), tBuSCS2− (3), (EtO)2PS2− (4)) and [Ru(CO)(η2-(Me2NCS2))(μ,η2-Me2NCS2)]2 (5). The lightly stabilized MeCN ligands of [Ru2(CO)4(MeCN)6][BF4]2 are replaced more readily than the bound acetate ligands of [Ru2(CO)4(μ-O2CMe)2(MeCN)2] by thiolates to produce cis-[Ru(CO)2(η2-(SS))2] with less selectivity. Structures 1 and 5 were determined by X-ray crystallography. Although the two chelating dithiolates are cis to each other in 1, the dithiolates are trans to each other in each of the {Ru(CO)(η2-Me2NCS2)2} fragment of 5. The dimeric product 5 can be prepared alternatively from the decarbonylation reaction of 1 with a suitable amount of Me3NO in MeCN. However, the dimer [Ru(CO)(η2-Et2NCS2)(μ,η2-Et2NCS2)]2 (6), prepared from the reaction of 2 with Me3NO, has a structure different from 5. The spectral data of 6 probably indicate that the two chelating dithiolates are cis to each other in one {Ru(CO)(η2-Et2NCS2)2}fragment but trans in the other. Both 5 and 6 react readily at ambient temperature with benzyl isocyanide to yield cis-[Ru(CO)(CNCH2Ph)(η2-(SS))2] ((SS)=Me2NCS2− (7) and Et2NCS2− (8)). A dimerization pathway for cis-[Ru(CO)2(η2-(SS))2] via decabonylation and isomerization is proposed. 相似文献
18.
Novel anionic dinuclear mixed-ligand peroxo complexes of the type [(UO2)2(O2)3L(H2O)2]3− (L = Histidinate, aspartate, salicylate, Imidazolate and glutamate) have been synthesized from the interaction of uranyl ion (UO22+) with peroxide (O22−) in the presence of the respective coligand (L) at pH 9–10. The sparingly soluble complexes were characterized by elemental analyses, FT-IR, laser Raman (LR) and UV-vis spectroscopy and solution electrical conductance measurements. Based on these studies, a double bridged dinuclear structure involving one peroxo and the mixed ligand L (via-COO−) has been tentatively proposed. Infra-red coupled with LR spectra evidenced structurally different metal bound peroxides (ν2 and σ:σ). An aqueous solution of the salicylate and aspartate complexes have been shown to convert triphenylphosphine (PPh3), cyclohexene, styrene and SO2 to the corresponding OPPh3, 1,2 cyclohexanediol, phenylethyleneglycol and SO42−, respectively. 相似文献
19.
在水热体系中合成了3个中心金属为镍离子, 以六配位扭曲八面体构型形成的具有螺旋结构的配位聚合物{[Ni2L2(bib)2·2H2O]·5H2O}n(1), [Ni2L2(bpy)]n(2)和{[Ni2L2(bibpip)2·2H2O]·6H2O}n(3)[H2L=4,4'-三苯胺二甲酸; bib=1,3-二(咪唑基)苯; bpy=4,4-联吡啶; bibpip=1,4-二(4-咪唑苄基)哌嗪]. 通过单晶及粉末X射线衍射、 红外光谱、 元素分析和热重分析对这3种化合物进行了表征. 结果表明, 化合物1属于单斜晶系, C2/c空间群, 其骨架为具有{42·65·8}拓扑结构的二维层结构; 化合物2属于斜方晶系, Fdd2空间群, 其骨架为具有{48·54·63}拓扑结构的三维超分子网络; 化合物3属于三斜晶系, P 空间群, 为1个五重穿插的三维超分子网络, 其骨架具有{44·62}拓扑结构. 相似文献
20.
When heated under reflux in CH2Cl2 solution with [Os(CO)3Cl2]2, two nido-[B9H12]− units edge-fuse to form anti-[B18H21]−. 相似文献