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2.
Michael I Bruce Andrew C Meier Allan H White 《Journal of organometallic chemistry》2004,689(5):965-970
The reaction between Ru3(μ-H){μ3-C2CPh2(OH)}(CO)9 and HCCPh, carried out in the presence of HBF4 · Me2O, afforded the cluster complexes Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 (5) and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8 (6), both of which were characterised by single-crystal X-ray studies. 相似文献
3.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2006,691(9):2048-2054
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (4) reacts with refluxing toluene to form the clusters Ru2Os3(μ-H)2(CO)16 (5) RuOs3(CO)9(μ-CO)2(η6-C6H5Me) (6) and Ru2Os3(CO)12(μ-CO)(η6-C6H5Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated. 相似文献
4.
Yu. V. Torubaev A. A. Pasynskii P. Mathur 《Russian Journal of Coordination Chemistry》2009,35(11):807-811
Reactions of Ru3(CO)12 with PhTeBr3 and of Re(CO)5Cl with PhTeI in benzene give the stable complexes (CO)2RuBr2(PhTeBr)2 (I) and (CO)3Re(PhTeI)3(μ3-I) (II) containing two and three ligands PhTeX (X = Br or I), respectively. The bonds between these ligands and the central metal
atom are fairly shortened (on average, Ru-Te, 2.608 ?; Re-Te, 2.7554(12)-2.7634(13) ?). The Te-X bonds in the ligands PhTeBr
(2.5163(5) ?) and PhTeI (2.7893(15) ?) are not lengthened appreciably. In complex II, the iodide anion is not coordinated by rhenium, yet being attached through weak secondary bonds to three Te atoms of the
three ligands PhTeI. 相似文献
5.
A new polymer azido-bridged copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]
n
(I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2], in which the azido ions display three different bridging modes. 相似文献
6.
Michael I. Bruce Paul A. Humphrey Allan H. White 《Journal of organometallic chemistry》2004,689(15):2558-2561
The reaction between AuMe(PPh3) and Ru3(μ-H)3(μ3-CBr)(CO)9 (1) affords the novel heptanuclear cluster Au4Ru3(μ3-CMe)(Br)(CO)9(PPh3)3 (2), containing an Au/Ru3/Au trigonal pyramidal cluster face-capped by two Au(PPh3) groups and a CMe ligand, together with Au2Ru3(μ-H)(μ3-CMe)(CO)9(PPh3)2 (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh3) groups. The latter co-crystallises with the analogous μ3-CH complex, as also shown spectroscopically. 相似文献
7.
Leonard Joachim Pereira 《Journal of organometallic chemistry》2005,690(4):1033-1043
TMNO-activated reaction of the heteronuclear cluster Os3Ru(μ-H)2(CO)13 (1) with diphenylphosphine afforded the novel phosphido-bridged clusters Os3Ru(μ-PPh2)(μ-H)3(CO)11 (2), Os3Ru(μ-PPh2)2(μ-H)2(CO)10 (3), Os3Ru(μ-PPh2)2(μ-H)4(CO)9 (4), and Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh2H) (5). The formation of 2-5 proceeded via P-H bond cleavage in the adduct Os3Ru(μ-H)2(CO)12(PPh2H) (6). Reaction of 2 with PPh3 afforded the adduct Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh3) (7) and the substituted derivative Os3Ru(μ-PPh2)(μ-H)3(CO)10(PPh3) (8). 相似文献
8.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2007,692(4):768-773
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) reacts with indene under thermal activation to afford the novel clusters RuOs3(μ-H)(CO)9(μ-CO)2(η5-C9H7) (3), RuOs3(μ-H)(CO)9(μ3,η5:η2:η2-C9H7) (4) and Ru2Os3(μ-H)(CO)11(μ3,η5:η2:η2-C9H7) (5), the latter two possessing indenyl ligands in the μ3,η5:η2:η2 bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated. 相似文献
9.
Richard D. Adams Erin M. Boswell Shaobin Miao Charles Edwin Webster Michael B. Hall Narpinder Kaur 《Journal of organometallic chemistry》2008,693(16):2732-2738
Two new compounds CpFeMn2(CO)7(μ3-S2)2 (2) and Cp3Fe3Mn(CO)4(μ3-S2)2(μ3-S) (3) were obtained by the treatment of [CpFeMn(CO)5(μ3-S2)]2 (1) with CO at room temperature in the presence of room light. Compound 2 contains two triply bridging disulfido ligands on opposite sides of an open FeMn2 triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements show that it is paramagnetic with one unpaired electron per formula equivalent. The electronic structure of 2 was established by DFT and Fenske-Hall (FH) molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital that is located principally on the iron atom. The cyclic voltammogram of 2 exhibits one reversible one-electron oxidation wave at +0.34 V and one irreversible one-electron reduction wave at −0.66 V vs. Ag/AgCl. Compound 3 contains three iron atoms and one manganese atom with two triply bridging disulfido ligands and one triply bridging sulfido ligand and has no unpaired electrons. The molecular structures of compounds 2 and 3 were established by single crystal X-ray diffraction analyses. 相似文献
10.
Relativistic scalar and spin-orbit density functional calculations of the electronic structure, Nucleus-Independent Chemical Shift (NICS) index and ELF function of the [Re2(CO)8(μ-BiPh)2] and [Re2(CO)8(μ-BiPh2)2] clusters are reported. We show here that the [Re2(CO)8(μ-BiPh)2] cluster has large negative NICS values in the region defined by the Re-Bi-Re-Bi four-membered ring and the ELF function shows significant electron delocalization density in the center of the metallic ring, thus indicating an aromatic cluster. In contrast the Re-Bi-Re-Bi four-membered ring in the [Re2(CO)8(μ-BiPh2)2] cluster has negligible paratropic ring currents and the ELF function shows a low-density region within the metallic ring indicating that aromaticity is switched off. However, the phenyl ligands in both clusters show the expected aromatic character. 相似文献
11.
Gloria Sánchez-Cabrera Francisco J. Zuno-Cruz María J. Rosales-Hoz 《Journal of organometallic chemistry》2007,692(11):2138-2147
The compound [Os3(CO)10(μ-Cl)(μ-AuPPh3)] (2) was prepared from the reaction between [Os3(CO)10(NCMe)2] (1) and [AuClPPh3] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os3(CO)10(μ-H)(μ-SC5H4N)] (4), formed by isolobal replacement of the fragment [AuPPh3]+ by H+ and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (5). [Os3(CO)10(μ-H)(μ-SC5H4N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies. 相似文献
12.
Oxo/hydoxo zirconium(IV) complex of the general formula [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9(μ2-OH)3]2 has been isolated, when Zr(OiPr)4 reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P63/m (no. 176)). Structure consists of dimers composed of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9] sub-units, linked by six μ2-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ2-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9(μ2-OH)3]2 proceeds with complete conversion to ZrO2 (monoclinic form) between 603 and 803 K. 相似文献
13.
I. V. Anan’ev M. A. Yakovleva E. V. Perova S. E. Nefedov 《Russian Journal of Inorganic Chemistry》2010,55(7):1057-1063
The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with a triethylamine excess to
form the trinuclear complex Co3(μ-OOCPh)4(μ,η2-OOCPh)2[OC(Ph)OHNEt3]2, and its reaction with 3,5-dimethylpyrazole yields the mononuclear complex Co(Hdmpz)2(OOCPh)2. The compound structures are discussed on the basis of X-ray crystallographic data. 相似文献
14.
Dafa Chen 《Journal of organometallic chemistry》2006,691(18):3823-3833
Thermal treatment of C9H7SiMe2C9H7 and C9H7Me2SiOSiMe2C9H7 with Ru3(CO)12 in refluxing xylene gave the corresponding diruthenium complexes (E)[(η5-C9H6)Ru(CO)]2(μ-CO)2 [E = Me2Si (1), Me2SiOSiMe2 (2)]. A desilylation product [(η5-C9H7)Ru(CO)]2(μ-CO)2 (3) was also obtained in the latter case. Similar treatment of C9H7Me2SiSiMe2C9H7 with Ru3(CO)12 gave a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η5:η2:η2-C9H7)2 (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me2SiSiMe2)[(η5-C9H6)Ru(CO)]2(μ-CO)2 (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me2Si)(η5-C9H6)Ru(CO)2]2 (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction. 相似文献
15.
Charles E. Ellul 《Journal of organometallic chemistry》2010,695(1):6-2376
The reduction of trans-[Pd(NHC)2Cl2] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IiPr2 = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd3(μ-CO)3(NHC)3] (NHC = IMes, 1; IiPr2, 3). Treatment of 1 with SO2 at room temperature yields the bridging SO2 complex [Pd3(μ-SO2)3(IMes)3] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography. 相似文献
16.
Crystal structure of a tetrahedral cluster complex [Zn2(NH3)6(μ-OH)][Zn(NH3)4]0.5[Re4Te4(CN)12]·5H2O
A cluster complex of the composition [Zn2(NH3)6(μ-OH)][Zn(NH3)4]0.5[Re4Te4(CN)12]·5H2O is obtained by the interaction of an aqueous solution of K4[Re4Te4(CN)12]·5H2O with an aqueous ammonia solution of ZnCl2. The compound crystallizes in the C2/m (12) monoclinic space group with unit cell parameters a = 23.233(2) ?, b = 14.5906(16) ?, c = 14.3825(15) ?, β = 125.169(1)°, V = 3985.5(7) ?3, Z = 4, d
x = 3.290 g/cm3. The structure is built from cluster [Re4Te4(CN)12]4− anions and complex [Zn2(NH3)6(μ-OH)]3+ and [Zn(NH3)4]2+ cations; the latter is disordered over two positions. 相似文献
17.
The title complex is obtained by reacting Ru3(CO)12 with 1,4-dichloro-but-2-yne (ClCH2CCCH2Cl, DCB) in CH3OH/KOH solution (followed by acidification with HCl). The X-ray structure analysis shows that (μ-H)2Ru3(CO)9{μ3-η2-[H2CC(H)CCC(O)OCH3]} complex contains a “parallel” ene-yne acetyl substituent, H2CC(H)CCC(O)OCH3; the formation of such a ligand starting from DCB is - to our knowledge - unprecedented. The synthesis of complex (μ-H)2Ru3(CO)9{μ3-η2-[H2CC(H)CCC(O)OCH3]} occurs through the activation of CO and methanol. This process has been found for other reactions of functionalized alkynes with M3(CO)12 carbonyls (M = Fe, Ru) under basic methanolic conditions.The known hydridic cluster, (μ-H)Ru3(CO)9[μ3-η3-(MeCCHCH)] has been identified as the minor reaction product. 相似文献
18.
Francesco Avanzini Maurizio Casarin Daniel Forrer Luciano Pandolfo Mauro Sambi Andrea Vittadini 《Theoretical chemistry accounts》2012,131(3):1166
Experimental and theoretical results pertaining to [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3], a possible molecular model of ZnS S-terminated polar surfaces, as well as a potential source of strictly monodispersed
ZnS quantum dots, are presented and discussed. The results of density functional theory (DFT) calculations provided a rationale
for the peculiar arrangement of [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3] clusters in the solid state, contemporarily indicating the unsuitability of the isolated species to mimic whatever (polar
or non-polar) ZnS surface. Despite the fact that such a failure is further confirmed by time-dependent DFT and UV–Vis diffuse
reflectance spectroscopy, the combined use of theoretical outcomes, DRIFT measurements, and literature data pertaining to
the surface chemical properties of ZnS (Hertl in Langmuir 4:594, 1988) ultimately testifies that [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3] is perfectly suited to model the interaction of pyridine molecules with ZnS surface Lewis acid sites. The herein reported
theoretical results are expected to be a useful reference for the interpretation of chemisorption experiments of Py-based
Lewis bases on single crystal ZnS surfaces. 相似文献
19.
Piotr Buchalski Janusz Lipkowski Antoni Pietrzykowski 《Journal of organometallic chemistry》2006,691(26):5825-5830
A novel tetrahedral (μ3-alkylidyne)tetranickel cluster (NiCp)4(μ3-C(CH2)4CH3) (4) was obtained in the reaction of nickelocene with potassium and 1-hexene. Compound 4 was characterised by means of MS and X-ray diffraction analysis. It crystallizes in the orthorhombic crystal system and Pna21 (No. 33) space group. Unit cell dimensions: a = 28.406(6) Å, b = 8.928(2) Å, c = 9.541(2) Å; Z = 4. The compound possesses 63 valence electrons, three more than the expected “magic number” for such type of clusters, and three of the four nickel atoms do not fulfil the 18VE rule. It is paramagnetic with the magnetic moment 3.54 μB, what corresponds to three unpaired electrons per molecule. This was confirmed by molecular orbital calculations using the density functional theory (DFT). 相似文献
20.
Giuliana Gervasio Domenica Marabello Andrea Secco 《Journal of organometallic chemistry》2005,690(16):3730-3736
The title compound has been obtained in considerable yield by reacting Ru3(CO)12 with 2-pentynal-diethyl-acetal [CH3CH2CCC(H)(OEt)2] (PDA) in hydrocarbon solvents. The X-ray analysis shows that the title complex belongs to the well known family of the flyover derivatives. Some X-ray structural studies have been reported, many years ago, on di-iron flyover complexes; in contrast only a few examples of diruthenium derivatives have been structurally characterized.The complex contains ethoxy-groups which could potentially undergo hydrolysis in the presence of tetraethyl-orthosilicate (TEOS) in the presence of catalysts. Reactions of complex Ru2(CO)6[μ-η4-{EtC2C(H)(OEt)2}CO{EtC2C(H)(OEt)2}] with TEOS in the presence of HCl or of NaF (as catalysts) have been attempted. An inorganic-organometallic sol-gel material containing the skeleton of the complex has been obtained and characterized with IR-Raman, XRD on powders and SEM microscopy. 相似文献