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1.
Two new mixed metal cluster complexes PtRu3(CO)10(PPh3)(3-S)2,3 14% yield and PtRu3(CO)9(PPh3)2(3-S)2,4 23% yield were obtained from the reaction of Ru3(CO)9(3-S)2,1 with Pt(PPh3)2(C2H4) at 0°C. The cluster of4 consists of a spiked triangle of four metal atoms with two triply bridging sulfido ligands. The reaction of Ru4(CO)11(4-S)2,2 with Pt(PPh3)2(C2H4) yielded the expanded mixed-metal cluster complex PtRu4(CO)12(PPh3)(4-S)2,5 in 12% yield. The structure of the cluster5 can be described as a pentagonal bipyramid of five metal atoms and two sulfido ligands with one metal-metal bond missing. Compounds4 and5 were characterized by a single-crystal X-ray diffraction analyses. 相似文献
2.
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
3.
The reaction of the unsymmetrical, coordinatively unsaturated dirhenium(II) complex [(XylNC)(OC)CIRe(μ-dppm)2ReCl2]O3SCF3 (dppm = Ph2PCH2PPh2) with one equivalent of XylNC in CH2Cl2 affords a fifth structural isomer of the [Re2Cl3(μ-dppm)2(CO)(CNXyl)2] + cation; this is believed to have a CO-bridged structure of the type [(XylNC)ClRe(μ-Cl)(μ-CO)(μ-dppm)2ReCl(CNXyl)]+. The latter complex reacts with a further equivalent of XylNC in the presence of Tl+ to form the [Re2Cl2(μ-dppm)2(CO)(CNXyl)3]2+ cation, which has been shown by IR spectroscopy, and by the X-ray crystallographic characterization of its neutral congener Re2Cl2(μ-dppm)2(CO)(CNXyl)3, to contain a very weak and unsymmetrical CO bridge. 相似文献
4.
The new platinum-osmium alkyne cluster complex Pt2Os4(CO)8(3-PhC2Ph)3 (
4-PhC2Ph),2, was obtained from the reaction of Pt2Os4(CO)18,1b, with PhC2Ph and was characterized by IR.1H NMR and single-crystal X-ray diffraction analyses. The cluster of compound2 consists of an osmium capped Pt2Os3 square pyramid. It aLso contains three triply bridging and one quadruply bridging diphenylacetylene ligands. Crystal data for2: space group PI,a = 12.530(2) Å,b = 21.565(4) Å,c = 11.284(2) Å, = 100.31(2), = 111.89(1), = 76.78(2),Z = 2, 3879 reflections,R = 0.032. 相似文献
5.
The reaction of the open bioctahedral form of Re(2)Cl(4)(&mgr;-dppm)(2)(CO)(CNXyl) (1), where XylNC = 2,6-dimethylphenyl isocyanide, with TlO(3)SCF(3) in the presence of acetonitrile proceeds with retention of stereochemistry at the dirhenium unit to afford the complex [Re(2)Cl(3)(&mgr;-dppm)(2)(CO)(CNXyl)(NCCH(3))]O(3)SCF(3) (3). The single-crystal X-ray structure determination of 3 shows that a Re&tbd1;Re bond is retained (the Re-Re distance is 2.378(3) ?) and that it is the chloride ligand trans to the XylNC ligand of 1 which is labilized. Complex 1 reacts with TlO(3)SCF(3) in a noncoordinating solvent to produce the unsymmetrical complex [Re(2)Cl(3)(&mgr;-dppm)(2)(CO)(CNXyl)]O(3)SCF(3) (2), through loss of this same chloride ligand of 1 and CO transfer from the adjacent Re center. The acetonitrile ligand of 3 is very labile and is readily displaced by XylNC and t-BuNC, with retention of stereochemistry, to produce complexes of stoichiometry [Re(2)Cl(3)(&mgr;-dppm)(2)(CO)(CNXyl)(CNR)]O(3)SCF(3) (R = Xyl, 4a; R = t-Bu, 4b). In a noncoordinating solvent, the nitrile ligand of 3 is lost and 2 is formed following CO transfer; this conversion is reversed upon the reaction of 2 with acetonitrile. When 3 is treated with CO, the acetonitrile ligand is again displaced, but in this instance the reaction is accompanied by a structure change to produce an edge-sharing bioctahedral complex of the type [Re(2)(&mgr;-CO)(&mgr;-Cl)(&mgr;-dppm)(2)Cl(2)(CO)(CNXyl)]O(3)SCF(3) (5). 相似文献
6.
David A. Kort Wengan Wu Phillip E. Fanwick Richard A. Walton 《Transition Metal Chemistry》1995,20(6):625-629
7.
We study the QCD corrections to the calculated values of σ(e+e-→ZH→Zbb), and find that for MH<100 GeV, the process can be measured at the LEP energy to extract information of Higgs and the QCD corrections are negligible, namely the tree-level calculation is sufficiently aciurate for the energy range, while for MH > 100 GeV, the Higgs-involved subprocess can only be investigated at NLC, and then the QCD correction becomes as large as 45%. For MH > 2mt, considering the subprocess e+e-→ZH→Ztt, the QCD corrections are also important and must be taken into account for the cross section evaluation. 相似文献
8.
Richard D. Adams Thomas Barnard Zhaoyang Li Wengan Wu John H. Yamamoto 《Journal of Cluster Science》1994,5(4):551-564
Abstarct The ten metal cluster complex Pt2Ru8(CO)23(µ3–H)2, 1 was found to react with EtC2Et to form a new ten metal tris-alkyne complex Pt2Ru8(CO)18(µ3–EtC2Et)2 (µ4–EtC2Et),2 in 35% yield. Complex 2 was characterized by IR,1H NMR , and single crystalx-ray diffraction analyses. The cluster can be viewed as a dodecahedron of eight metal atoms capped with two ruthenium carbonyl groups, two triply bridging EtC2Et ligands and one quadruply bridging EtC2Et ligand. Application of the standard electron counting procedures indicate that this is an unusual complex in which the 18 electron rule applies and the polyhedral skeletal electron pair theory does not. Crystal Data for 2 2.0.5 CH2CI2: space group = P21,a = 12.759(2) A,b=18.438(2)Å,c = 20.197(3) Å, = 91.59(1)°, Z. = 4, 6394 reflections,R = 0.037. 相似文献
9.
The monocarbonyl complex Re2Cl4(µ-dppm)2(CO) reacts with xylyl isocyanide in acetonitrile to afford the bioctahedral complex (CO)Cl2Re(µ-dppm)2 ReCl2(CNxyl), 2b. This is a different structural isomer from the edge-sharing bioctahedral complex Cl2Re(µ-Cl)(µ-dppm)2ReCl(CNxyl) or this same stoichiometry which A formed when acetone is be reaction solvent. The complex2b reacts with a further equivalent of xylNC in the presence of TlO3SCF3 in dichloromethane to form a red complex of composition [Re2Cl3(µ-dppm)2 (CO)(CNxyl)2]O3SCF3. 3, which has the open bioctahedral structure [(xylNC)2ClRe(µ-dppm)2ReCl2(CO)]O3SCF3. This is a third isomeric form of this dirhenium cation: the previously isolated green and yellow forms have edge-sharing bioctahedral structures. Crystal data for3 at 295 K: orthorhombic space group Pbca (No. 61) witha=22.654(5) Å,b=22.717(4) Å,c=27.324(4) A,V= 14061(7) Å3, andZ = 8. The structure was refined to R = 0.059 (R, = 0.134 ) for 14164 data. The Re-Re distance is 2.3833(8) Å. 相似文献
10.
Jean Bernard Ballif Pierre Braunstein Andrew D. Burrows Richard D. Adams Wengan Wuz 《Journal of Cluster Science》1994,5(3):443-466
The reaction of the ketophosphine ligand Ph2PCH2C(O)Ph (P~O) with [PtCl2(NCMe)2] and carbon monoxide in THF in the presence of an excess of zinc afforded the 70 electron pentanuclear cluster [Pt5(CO)(μ-CO)5(P~O)4] (1). Reaction of the palladium(0) complex [Pd2(dba)3] CHCl3 (dba = dibenzylideneacetone) with Ph2PCH2C(O)R [R = Ph or C5H4Fe(C5H5)] under SO2 led to the pentapalladium cluster compounds [Pd5(μ3-SO2)2 (μ-SO2)2 {Ph2PCH2C(O)R}5] (2a,R = Ph;2b,R = C5H4Fe(C5H5)), Cluster (1) reacts with 2,6-xylyl isocyanide, CNC6H3Me2-2,6 to give a red cluster of formula [Pt5(μ-CNC6H3Me2-2, 6)3 (CNC6H3Me2-2, 6)5 (P~O)2] (3) and a green complex (4). The corresponding complexes (6) and (7) were also obtained by using PPh3 instead of P~O. Clusters (2a) and (2b) react with [NEt3Bz] Cl to give[NEt3Bz][Pd3(μ-SO2)2 (μ-Cl){Ph2PCH2C(O)R}3](8a,R = Ph;8b,R = C5H4Fe(C5H5)). The molecular structures of (1) and (3) were determined by single-crystal X-ray diffraction analyses. 相似文献