共查询到20条相似文献,搜索用时 0 毫秒
1.
2.
3.
4.
The reaction of Na2[Fe(CO)4] with Br2CF2 in n‐pentane generates a mixture of the compounds (CO)3Fe(μ‐CO)3–n(μ‐CF2)nFe(CO)3 ( 2 , n = 2; 3 , n = 1) in low yields with 3 as the main product. 3 is obtained free from 2 by reacting Br2CF2 with Na2[Fe2(CO)8]. The non‐isolable monomeric complex (CO)4Fe=CF2 ( 1 ) can probably considered as the precursor for 2 . 3 reacts with PPh3 with replacement of two CO ligands to form Fe2(CO)6(μ‐CF2)(PPh3)2 ( 4 ). The complexes 2 – 4 were characterized by single crystal X‐ray diffraction. While the structure of 2 is strictly similar to that of Fe2(CO)9, the structure of 3 can better be described as a resulting from superposition of the two enantiomers 3 a and 3 b with two semibridging CO groups. Quantum chemical DFT calculations for the series (CO)3Fe(μCO)3–n(μ‐CF2)nFe(CO)3 (n = 0, 1, 2, 3) as well as for the corresponding (μ‐CH2) derivatives indicate that the progressively larger σ donor and π acceptor properties for the bridging ligands, in the order CO < CF2 < CH2, favor a stronger Fe–Fe bond. 相似文献
5.
6.
Halogeno-Bridged Heteronuclear Metal Atom Clusters of the Three Types Re2(CO)4L2(μ-X)2(μ-Y) (L = (C6H5)3P; X = Br, I; Y = GaRe(CO)4ax-L), Re2(CO)6L2(μ-X) (μ-GaX2) (X = I), and Re3(CO)9L3 (μ-X)3(μ3-Y) (X = Cl) The title compounds of the both types Re2(CO)4L(μ-X)2(μ-Y) [L = (C6H5)3P; X = Br, I; Y = GaRe(CO)4ax-L] and Re3(CO)9L3(μ-X)3 (μ3-Y) (X = Cl) were prepared by the reaction of GaX3 (X = Cl, Br, I) and Re2(CO)8(ax-L)2 in boiling mesitylene solution. The obtained substance Re2(CO)4L2(μ-I)2(μ-Y) and carbon monoxide gave the compound of the third type Re2(CO)6L2(μ-I)(μ- GaI2). The last-named single iodo-bridged dirhenium cluster could be therefore a precursor complex of the double iodo-bridged compound. The four diamagnetic substances were characterized by 31P n.m.r. spectroscopy and their molecular structures were acertained by X-ray measurements. The result of the single crystal X-ray analysis of Re2(CO)4L2(μ-Br)2 [μ-GaRe(CO)4ax-L], a bridged coordination octahedron pair with a common face, and that of the edge-bridged pair Re2(CO)6L2(μ-I)(μ-GaI2) each possessing a Re? Re bond are especially treated in the present work. 相似文献
7.
8.
Die Kristallstrukturen der Titelkomplexe, deren einer zwei verschiedene Carbonylmetall-Einheiten, deren anderer zwei verschiedene Brückenliganden besitzt, wurden bestimmt. Die Stereochemie des Cr? Ni-Komplexes entspricht der Erwartung, seine Metall—Metall-Bindung ist jedoch kürzer als der Durchschnittswert aus den entsprechenden Cr2- bzw. Ni2-Verbindungen. Bei dem Fe2-Komplex ist die Gesamt-Molekülgeometrie ebenfalls normal, doch der Metall—Metall-Abstand ist deutlich kürzer als erwartet. Die Verkürzung der Metall—Metall-Bindungen steht bei beiden Komplexen in Zusammenhang mit der Minimisierung der intramolekularen sterischen Hinderung. Stereochemistry of the Metal—Metal Bond. Structures of the Compounds (CO)4Cr[μ-PMe2]2Ni(CO)2 and (CO)3Fe[μ-PMe2, μ-I]Fe(CO)3. Each with Two Different Complex Halves The crystal structures of the title complexes, one of which has two different carbonylmetal units and the other has two different bridging ligands, were determined. The stereochemistry of the Cr? Ni complex is as expected, its metal—metal bond however is shorter than the average value of the corresponding Cr2 and Ni2 compounds. For the Fe2 complex the overall molecular geometry is also normal, but the metal—metal distance is considerably shorter than expected. The shortening of the metal—metal bonds is in both complexes correlated with the minimization of intramolecular steric strain. 相似文献
9.
10.
The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 Å3; Z=2, Dc=1.74 g/cm3. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH3C6H4C2S)(μ-n-C3H7S)Fe2(CO)6 with Co2(CO)8. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC3H7 is e-type, while that of —SC2C6H4CH3 is a-type. 相似文献
11.
12.
13.
14.
15.
16.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(5):903-908
Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], and [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] [Ru3Rh(CO)7(μ3‐H)(μ‐PtBu2)2(tBu2PH)(μ‐Cl)2] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) Å3. The reaction of 4 with dppm (Ph2PCH2PPh2) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 Å3. Moreover single crystals of [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P21/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) Å3. 相似文献
17.
18.
Reactions of aqueous HX (X?Cl, Br) or of AuCl(PPh3) with Ru5(μ5-C2PPh2)(μ-PPh2)(CO)13 result in addition of the 4e-donor set (H + X) or (Au(PPh3) + Cl) with concomitant opening of two Ru? Ru bonds to give complexes containing dimetallated triangular of ‘scorpion’ cores. Aqueous HI reacts similarly, but in this case the iodide ligand spans three Ru atoms, the (H + I) set acting as 6e-donor. The structures of the two title compounds were confirmed by X-ray crystallographic studies. Ru5(μ-H)(μ5-C2PPh2)(μ-PPh2)-(μ-Br)(CO)13 is triclinic, space group P1 , a = 9.689(2), b = 11.874(2), c = 20.005(4) Å, α = 84.66(2), β = 82.90(6), λ = 67.51(6)°, Z = 2; 6478 data with I > 2σ(I) were refined to R = 0.0368, Rw = 0.0362. Ru5(μ-H)(μ5-C2PPh2)(μ3-I)(μ-PPh2)-(CO)12.CH2Cl2 is monoclinic, space group P21/n, a = 14.809(4), b = 20.721(4), c = 17.698(5) Å, β = 111.42(2)°, Z = 4; 7815 data with I > 2σ(I) were refined to R = 0.0440, Rw = 0.0416. 相似文献
19.
20.
Synthesis and Crystal Structures of the Phosphaneimine Complexes [Cu(μ-HNPEt3)]4(O3S–CF3)4 and [Pt2Me6(μ-I)2(μ-HNPMe3)] The title compounds have been prepared by the reaction of copper(I)triflate with [NiBr(NPEt3)]4 in CH2Cl2 suspension in the presence of water, and by the reaction of [PtMe3I]4 with Me3SiNPMe3 in boiling toluene in the presence of cesium fluoride, respectively. According to the crystal structure determinations the cation of the copper complex forms tetrameric units [Cu(HNPEt3)]44+ with S4 symmetry with Cu–N bond lengths of 191.6 and 192.1 pm. In the platinum complex the platinum atoms are linked by two μ-I bridging atoms as well as by the μ-N atom of the HNPMe3 ligand with Pt–N bond lengths of 228.1 and 229.5 pm. 相似文献