共查询到20条相似文献,搜索用时 15 毫秒
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Brian F.G. Johnson David A. Kaner Jack Lewis Paul R. Raithby 《Journal of organometallic chemistry》1981,215(2):C33-C37
The reaction of [HOs3(CO)11]? with AuClPR3 (R Et, Ph) yields the complex HOs3Au(CO)10(PR3), and the PPh3 derivative has been characterised by an X-ray analysis; the structure is compared with that of Os3Au(CO)10(PPh3)-(SCN) and is shown to contain a formally unsaturated OsOs bond. 相似文献
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Os(CS)(PhC?CPh)(PPh3)2 is formed by the treatment of Os(CS)(CO)(PPh3)3 with diphenylacetylene and is an example of a complex containing a four-electron donor acetylene ligand. Os(CS)(PhC?CPh)(PPh3)2 crystallizes in the monoclinic space group P21/n with the cell dimensions a = 9.028(5), b = 25.256(2) and c = 19.22(2) Å with β = 103.8(7)°, V = 4260 Å3, Z = 4 and d(calcd) = 1.461 g cm?3 for mol.wt 937.09 g mol?1. Diffraction data were collected with a Nonius CAD-4 diffractometer and refined to R = 4.05% and Rw = 4.19% for 1172 independent reflections. The structure can be described as a distorted trigonal bipyramid with the CS ligand occupying an axial position. The two cis-PPh3 ligands are in equatorial sites with the acetylene occupying a position between the remaining axial and equatorial sites. The diphenylacetylene is symmetrically bound to the metal with an average Os? C distance of 2.04(3) Å. The Os? CS distance is unusually short at 1.79(2) Å. 相似文献
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Michael I. Bruce Omar bin Shawkataly Brian K. Nicholson 《Journal of organometallic chemistry》1985,286(3):427-437
H2Ru3(μ3-S)(CO)9 is deprotonated by K[HBBus3] to give cluster anions which react with [O{Au(PPh3)}3]+ or with AuCl(PPh3)/T1+ to give HRu3Au(μ3-S)(CO)9(PPh3) (1) and Ru3Au2(μ3-S)(CO)9(PPh3)2 (3). A similar sequence with HRu3(μ3-SBut)(CO)9 leads to Ru3Au(μ3-SBut)(CO)9(PPh3) (2) as the main product although some 1 also forms, indicating SC cleavage competes with deprotonation of HRu3(μ3-SBut)(CO)9 by [HBBus3]?. The X-ray crystal structures of 1, 2 and 3 are described; (1) and (2) have “butterfly” AuRu3 cores with markedly different hinge angles of 119 and 148° respectively, while 3 has a trigonal-bipyramidal Au2Ru3 skeleton. All three clusters have the sulphur atom symmetrically bridging the Ru3 triangular face. 相似文献
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《Journal of organometallic chemistry》1987,323(2):247-259
The reaction of trans-MeOIr(CO)(PPh3)2 with TCNE (tetracyanoethylene) gives rise to the stable adduct MeOIr(CO)(PPh3)2(TCNE), the structure of which has been determined via a single-crystal X-ray diffraction study. This complex crystallizes in the centrosymmetric orthorhombic space group Pbca (D152h; No. 61) with a 17.806(4), b 20.769(4), c 20.589(6) Å, V 7614(3) Å3 and Z = 8. Diffraction data (Mo-Kα, 2θ = 5–45°) were collected on a Syntex P21 automated four-circle diffractometer and the structure was solved and refined to RF 6.2% for 3502 data with |F0| > 3σ(|F0|) (RF 4.3% for those 2775 data with |F0| > 6 σ(|F0|)). The central iridium atom has a distorted trigonal bipyramidal coordination geometry in which the methoxy group (Ir-OMe 2.057(8) Å) and carbonyl ligand (Ir-CO 1.897(14) Å) occupy axial sites with ∠MeOIrCO 174.7(4)°. The two triphenylphosphine ligands occupy equatorial sites (IrP(1) 2.399(3), IrP(2) 2.390(3) Å, ∠P(1)IrP(2) 110.32(11)° and the TCNE ligand is linked in an η2 “face-on” fashion with the olefinic bond parallel to the equatorial coordination plane (IrC(4) 2.176(10), IrC(7) 2.160(12) Å) and lengthened substantially from its value in the free olefin (C(4)C(7) 1.539(17) Å). 相似文献
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Detailed procedures for the syntheses of Os(CO)2(PPh3)3, Os(CO)(CNR)-(PPh3)3 (R = p-tolyl), Os(CO)(CS)(PPh3)3 and Os(CS)(CNR)(PPh3)3, together with the derived complexes Os(CO)2(CS)(PPh3)2, Os(CO)(CS)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CNR)(PPh3)2, Os(η2-C2H4)(CO)(CS)(PPh3)2, Os(η2CS2)(CO)2-(PPh3)2, Os(η2CS2)(CO)(CS)(PPh3)2, Os(η2-CS2)(CO)(CNR)(PPh3)2, Os(η2PhC2Ph)(CO)2(PPh3)2 and OsH(C2Ph)(CO)2(PPh3)2 are described. 相似文献
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《Journal of organometallic chemistry》1991,401(3):C46-C49
The structure of [Os7(CO)20P(OMe)3] has been determined by an X-ray diffraction study. The metal-atom skeleton consists of a capped octahedron, in which the capping Os-atom bears the P(OMe)3 ligand and two terminal COs, while the other six Os-atoms bear three terminal COs each. 相似文献
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Summary Os2(CO)8Cl2
(1) is orthorhombic P212121 witha=9.3599(9),b=9.879(2),c=16.014(3), V=14803, Dc=3.03 Mgm–3 for Z=4. Structure solved by Patterson methods. Final R=0.038, Rw=0.038 [w=(2F)] for 1270 observed reflections and 141 parameters. Os3(CO)12Cl2
(2) is monoclinic C2/m witha=12.105(3), b=10.612(3),c=8.798(1) , =117.02(2)°, V=10063, Dc=3.22 Mgm–3 for Z=2. Structure solved by Patterson methods. Final R=0.036, Rw=0.037 (w=(2F)–) for 821 observed reflections and 75 parameters.Complex(1) has an osmium-osmium single bond 2.897(1), with the chloride ligands in equatorial positions,(2) has a linear triosmium chain with osmium-osmium single bonds 2.893(1) and the chloride ligands occupy equatorial sites on the terminal osmium atoms. Both(1) and(2) are isostructural with their osmium carbonyl iodide analogues. 相似文献
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The carbonylation of Os2(CO)10[-CH2N(Me)C(Et)](-H),1 at 110°C/1300 psi has yielded the carbene complex Os3(CO)11[C(Et)NMe2],2, the first simple carbene derivative of Os3(CO)12, in 68% yield. Compound2 was characterized by a single crystal structure analysis which showed the position of a dimethylaminocarbene ligand in an equatorial coordination site. Compound2 is decarbonylated at 97°C to reform1 in 59% yield. Compound1 can be decarbonylated further at 125°C to yield the new compound Os3(CO)9 [3-2-C(H)N(Me)C(Et)](-H)2,3 in 94% yield. Compound3 was characterized by a crystal structure analysis and was shown to possess a triply bridging C(H)N(Me)C(Et) ligand containing two carbene centers. Compounds1 and2 can be regenerated from3 by carbonylation with CO at 110°C/800 psi. The facile activation of the N-methyl CH bonds of the carbene ligand of2 is produced by the metal atoms adjacent to the carbene coordination site, and may be a characteristic feature of the chemistry of carbene ligands in clusters. For2: space group=P
,a=11.407(2) Å,b=12.332(2) Å,c=8.602(1) Å, =103.92(1), =110.56(1)°, =82.57(1),Z=2, 2627 reflections,R=0.031; for3: space group=C2/c,a=17.160(3) Å,b=8.947(2) Å,c=27.034(6) Å, =97.82(1)°,Z=8, 2044 reflections,R=0.038. 相似文献
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[OS(η2-CS2Me)(CO)2(PPH3)2]+ and [Ir(η2-CS2Me)Cl(CO)(PPh3)2)+ react with NaBH4 giving OsH(CS2Me)(CO)2(PPh3)2 and IrH(CS2Me)Cl(CO)(PPh3)2 respectively; These compounds contain mutually hydride and η1-dithiomethylester ligands and upon heating undergo 1,2-elimination of MeSH producing Os(CS)(CO)2(PPh3)2 and IrCl(CS)(PPh3)2. 相似文献
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E. D. Korniets L. K. Kedrova N. I. Pavlenko P. P. Semyannikov 《Russian Chemical Bulletin》1988,37(6):1222-1224
Conclusions During the action of triphenylphosphine on Os3(-H)(vt-O2CCF3)(CO)10 the substitution of the trifluoroacetate ligand and the substitution of one CO group take place in parallel with the formation of the clusters Os3(-H)(O2CCF3)(CO)10(PPh3) and Os3(-H)(-O2CCF3)(CO)9 (PPh3). In the reaction of the cluster Os3(-H)(-O2CCH3)(CO)10 with triphenylphosphine only Os3(-H)(-O2CCH3)(CO)9(PPh3) is formed with a quantitative yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1388–1390, June, 1988. 相似文献
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《Chemical physics letters》1985,115(6):515-518
High-valence osmium ions (Os5+ or Os7+) were stabilized on CeO2 and ThO2, when the initially impregnated cluster Os3(CO)12 was decomposed under oxidizing conditions. This is in contrast to the formation of low-valence ions (Os1+ and Os3+) on Al2O3. The presence of osmium on CeO2 and ThO2 presumably modified their redox properties and created new centers for O2− radical anion localization. 相似文献
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《Journal of Coordination Chemistry》2012,65(12):2202-2213
[ReBr2(O)(OCH3)(PPh3)2] has been obtained in the reaction of [ReBr3O(PPh3)2] or [ReBr2(η2-N2COPh-N′,O)(PPh3)2] with an excess of methanol. [ReBr2O(OMe)(PPh3)2] crystallizes in the triclinic space group P-1. The complex was characterized by infrared, UV-Vis, and 1H NMR spectra. The electronic structure of the obtained compound has been calculated using the DFT/TD–DFT method. 相似文献
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《Polyhedron》1999,18(20):2625-2631
Treatment of RuHCl(CO)(L)3 with a slight excess amount of K[HB(3,5-Me2pz)3] in boiling MeOH solution yielded unusual 3,5-dimethylpyrzaole (Hdmpz) complexes, RuHCl(CO)(Hdmpz)(L)2 (L=PPh3, 1 or AsPh3, 2). Unexpectedly the dissociation of the bonds between the boron atom and the nitrogen atoms of the potentially tridentate [HB(3,5-Me2pz)3]− ligand during the coordination of the ligand to the RuII metal has been observed. In a separate preparation, the RuHCl(CO)(Hdmpz)(PPh3)2 complex has also been synthesized from the reaction between RuHCl(CO)(PPh3)3 and the monodentate Hdmpz ligand. Complexes 1 and 2 have been characterized by elemental analysis, IR and 1H NMR spectroscopies. Compound 1 has also been prepared by the reaction between RuHCl(CO)(PPh3)3 and K[H2B(3,5-Me2pz)2] in boiling toluene solution. The crystal structure of 2 has been studied by X-ray crystallography. The geometrical structure around RuII of 2 is a distorted octahedral structure. The crystal structure of 2 consists of a discrete monomeric compound. It is interesting to find that the sterically-demanding [HB(3,5-Me2pz)3]− or [H2B(3,5-Me2pz)2]− ligands break up during the reaction with the RuII complexes to form the neutral 3,5-dimethylpyrazole complexes. In contrast to these observations, [H2Bpz2]− and [H2B(4-Brpz)2]− ligands form very stable RuII complexes. 相似文献
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Zain Dawoodi Martin J. Mays Paul R. Raithby 《Journal of organometallic chemistry》1981,219(1):103-113
The reaction of H2Os3(CO)10 with CF3CN in hexane at 80°C leads to two isomeric products. The isomer constituting the major product contains a 1,1,1-tri-fluoroethylidenimido ligand which bridges one edge of the Os3 triangle via the nitrogen, atom and may be formulated as (μ-H)Os3(CO)10(μ-NC(H)CF3) (I). The minor product, formulated as (μ-H)Os3(CO)10(μ-η2-HNCCF3) (II), contains a 1,1,1-trifluoroacetimidoyl ligand which is also edge-bridging, being N-bonded to one Os atom and C-bonded to the other. Thermolysis of I and II in solution results in loss of a CO group in each case to give (μ-H)Os3(CO)9? (μ3-η2-NC(H)CF3) (III) and (μ-H)Os3(CO)9(μ3-η2-HNCCF3) (IV), respectively, which, it is proposed, are structurally related to I and II, but with the CN group coordinated also to the third Os atom in place of a CO group. In the case of IV this proposal has been confirmed by an X-ray crystallographic analysis. The compound crystallises in space group C2/c with a = 14.258(7), b = 13.486(10), c = 18.193(8) Å, β = 92.68(4)°, and Z = 8. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by full-matrix least squares to R = 0.054 for 2489 unique observed diffractometer data. Reaction of I with Et3P gives a 1 : 2 adduct which is formulated as (μ-H)Os3(CO)10[μ-N?C(H)(CF3)PEt3] (V) on the basis of NMR evidence. 相似文献
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《Journal of organometallic chemistry》1987,319(3):411-422
The reaction of C2(CO2Me)2 with trans-MeIr(CO)(PPh3)2 leads to a kinetic isomer which has been characterized by 1H and 31P NMR and infrared spectra and to a thermodynamic isomer which has been characterized by 1H and 31P NMR, infrared, microanalysis and X-ray crystallography. The isomerization occurs readily in solution at room temperature; somewhat more slowly at −20°C. The thermodynamically stable isomer of MeIr(CO)(PPh3)2[C2(CO2Me)2] crystallizes in the centrosymmetric monoclinic space group P21/c with a 14.847(2), b 16.648(2), c 15.656(3) Å, β 90.595(14)°, V 3869.7(11) Å3 and Z = 4. Single-crystal X-ray diffraction data were collected with a Syntex P21 automated diffractometer (Mo-Kα radiation, 2θ 5–40°) and the structure was solved and refined to RF 8.6% for all 3631 independent data (RF 4.0% for those 2318 data with |Fo| > 6σ(|Fo|)). The IrI center has a trigonal-bipyramidal environment with the methyl ligand and one PPh3 ligand occupying axial sites (Ir-Me 2.193(14), Ir-P(1) 2.425(4) Å). The C2(CO2Me)2 ligand is π-bonded to the iridium atom and lies with its triple bond parallel to the equatorial coordination plane; the equatorial ligands are completed by the second PPh3 ligand (Ir-P(2) 2.402(3) Å) and a CO ligand (Ir-CO 1.812(15) Å). 相似文献
17.
Marjorie M. Harding Barry S. Nicholls Anthony K. Smith 《Journal of organometallic chemistry》1982,226(1):C17-C20
Reaction of Ru3(CO)12 with HC(PPh2)3 leads to a variety of products, two of which have been characterised. One is the symmetrically capped product Ru3(CO)9[HC(PPh2)3], which was characterised spectroscopically. The second product was characterised crystallographically as Ru3(CO)9[HC(PPh2)-(PhPC6H4PPh)]-CHCl3. 相似文献
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Summary RuH2(CO)(PPh3)3 was prepared in a CO2 and H2 atmosphere from RuCl3 and PPh3 in the presence of alcohol and Et3N. Introduction of CO into the system lead to the formation of other complexes e.g. Ru(CO)3-(PPh3)2. Addition of alkali in place of Et3N resulted in a decrease in the RuH2(CO)(PPh3)3 yield.Author to whom all correspondence should be directed. 相似文献