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1.
Dielmann F Schindler A Scheuermayer S Bai J Merkle R Zabel M Virovets AV Peresypkina EV Brunklaus G Eckert H Scheer M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(4):1168-1179
Slow diffusion reactions of the pentaphosphaferrocene [Cp*Fe(η(5)-P(5))] (Cp*=η(5)-C(5)Me(5) (1)) with CuX (X=Cl, Br, I) in different stoichiometric ratios and solvent mixtures result in the formation of one- and two-dimensional polymeric compounds 2-6 with molecular formula [{Cu(μ-X)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (X=Cl (2a), I (2'c)), [{Cu(μ-I)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (3), [{CuX}{Cp*Fe(μ(4),η(5):η(1):η(1):η(1)-P(5))}](n) (X=Cl (4a), Br (4b), I (4c), Br (4'b), I (4'c)), [{Cu(3)(μ-I)(2)(μ(3)-I)}{Cp*Fe(μ(5),η(5):η(1):η(1):η(1):η(1)-P(5))}](n) (5) and [{Cu(4)(μ-X)(4)(CH(3)CN)}{Cp*Fe(μ(7),η(5):η(2):η(1):η(1):η(1):η(1):η(1)-P(5))}](n) (X=Cl (6a), Br (6b)), respectively. The polymeric compounds have been characterised by single-crystal X-ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solid-state structures demonstrate the versatile coordination modes of the cyclo-P(5) ligand of 1, extending from two to five coordinating phosphorus atoms in either σ or σ-and-π fashion. In compounds 2a, 2'c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2a, 2'c) and an unprecedented 1,3 coordination mode (3) to form one-dimensional polymers. Compounds 4a-c, 4'b, 4'c and 5 represent two-dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo-P(5) ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6a,b display a tilted tube, in which all P atoms of the cyclo-P(5) ligand are coordinated to copper atoms in σ- and π-bonding modes. 相似文献
2.
Andrea Schindler Gábor Balázs Manfred Zabel Christian Gröger Robert Kalbitzer Manfred Scheer 《Comptes Rendus Chimie》2010,13(8-9):1241-1248
The reaction of the 1,2,4-triphosphaferrocene [Cp*Fe(η5-P3C2tBu2)] (1) with CuX (X = Cl, Br, I) in a 1:1 stoichiometric ratio leads to the formation of the oligomeric compounds [{Cu(μ-X)}6(μ6-X)Cu(MeCN)3{μ,η2-(Cp*Fe(η5-P3C2tBu2))}2{μ3,η3-(Cp*Fe(η5-P3C2tBu2))}] (X = Cl (2), Br (3)) and [{Cu(μ-I)}3{Cu(μ3-I)}3Cu(μ6-I){μ,η2-(Cp*Fe(η5-P3C2tBu2))}3{η1-(Cp*Fe(η5-P3C2tBu2))}] (4) revealing Cu(I) halide cages surrounded by 1,2,4-triphosphaferrocene moieties. The reaction of [Cp*Fe(η5-P3C2tBu2)] with CuI in a 1:4 stoichiometry leads to the formation of the two-dimensional polymer [{Cu(μ-I)}4{Cu(μ3-I)(MeCN)}2{μ3,η3-(Cp*Fe(P3C2tBu2))}]n (5). The oligomeric compounds show dynamic behavior in solution monitored by 31P NMR spectroscopy. All compounds are additionally characterized by single crystal X-ray diffraction. 相似文献
3.
The title complex [Cp*Ru(η6-C6H5BPh3)] has been synthesized by the reaction of [Cp*Ru(H2O)(NBD)]BF4 with H2 and NaBPh4, and its crystal structure was determined by singlecrystal X-ray diffraction analysis. It crystallizes in triclinic, space group P(1) with a = 11.0610(10), b = 11.2317(10), c = 12.3633(11) (A), α = 81.419(2), β = 67.8370(10), γ = 88.370(2)°, V= 1405.9(2) (A)3,Z= 2, C34H35BRu, Mr= 555.50, Dc = 1.312 g/cm3, F(000) = 576 and μ(MoKa) = 0.577 mm-1. The final R and wR are 0.0559 and 0.1483, respectively for 4365 observed reflections with I > 2σ(Ⅰ). In the title complex, the four phenyl rings bonded to the B atom are deposited in a tetrahedral geometry,and one of the phenyl rings is η6-bonded to ruthenium. 相似文献
4.
5.
《Journal of organometallic chemistry》1998,571(2):289-295
Antimony is reduced when [SbPh2BrO]2 is treated with Na[Mo(CO)3(η5-C5H5)] to produce [μ-SbPh2]2[Mo(CO)2(η5-C5H5)]2. A structure determination shows diphenylstibido groups bridging between two Mo(CO)2(η5-C5H5) moieties giving a central ‘butterfly’ shaped Sb2Mo2 ring. The cyclopentadiene rings are trans to each other and Mo–Sb and Sb–Sb separations are both short. An iron analogue could not be obtained from [SbPh2BrO]2 and Na[Fe(CO)2(η5-C5H5)] but a mixture of SbPh[Fe(CO)2(η5-C5H5)]2 and SbPh2[Fe(CO)2(η5-C5H5)] was obtained using SbPh2Cl. An X-ray structure for SbPh[Fe(CO)2(η5-C5H5)]2 shows an open stibinidine structure. 相似文献
6.
Sebastian Heinl Gábor Balázs 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):924-932
AbstractA new synthesis of [CpBIGFe(CO)2]2 3 (CpBIG = C5(4-nBuC6H4)5) was developed starting from CpBIGNa and FeCl2 in the presence of CO. Reaction of this product with P4 leads to the two new Pn ligand complexes [CpBIGFe(η5-P5)] 1b and [(CpBIGFe)2(μ,η4:4-P4)] (4) containing the highly sterically demanding CpBIG ligand. Depending on the solvent, different ratios of 1b:4 are obtained. The products 1b, 3, and 4 were characterized by spectroscopic methods as well as by X-ray diffraction. 相似文献
7.
《Journal of organometallic chemistry》1987,335(1):91-95
An X-ray diffraction study has shown that tetracarbonyl[η4-(1,1,3,4-tetramethyl- silole)]chromium has a conjugated 1,3-diene bonded to a distorted piano stool Cr(CO)4 fragment. The intra-ring CC bond lengths (139.2, 145.8 and 139.0 pm) indicate predominant diene-to-metal donor bonding. The bending angle of the silole ligand is 37.7°, and the Cr(CO)2 trans angles are 105.87 and 149.12°. 相似文献
8.
Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres. 相似文献
9.
Dr. Claudia Heinl Dr. Eugenia Peresypkina Dr. Gábor Balázs Dr. Eric Mädl Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(27):7542-7548
The so far missing parent compound of the large family of pentaphosphaferrocenes [CpFe(η5-P5)] ( 1 b ) was synthesized by the thermolysis of [CpFe(CO)2]2 with P4 using the very high-boiling solvent diisopropylbenzene. It was comprehensively characterized by, inter alia, NMR spectroscopy, single crystal X-ray structure analysis, cyclic voltammetry and DFT computations. Moreover, its coordination behavior towards CuI halides was explored, revealing the unprecedented 2D polymeric networks [{CpFe(η5:1:1:1:1-P5)}Cu2(μ-X)2]n ( 2 a : X=Cl, 2 b : X=Br) and [{CpFe(η5:1:1-P5)}Cu(μ-I)]n ( 3 ) and even the first cyclo-P5-containing 3D coordination polymer [{CpFe(η5:1:1-P5)}Cu(μ-I)]n ( 4 ). The sandwich complex 1 b can also be incorporated in nano-sized supramolecules based on [Cp*Fe(η5-P5)] ( 1 a ) and CuX (X=Cl, Br, I): [CpFe(η5-P5)]@[{Cp*Fe(η5-P5)}12(CuX)20-n] ( 5 a : X=Cl, n=2.4; 5 b : X=Br, n=2.4; 5 c : X=I, n=0.95). Thereby, the formation of the CuI-containing fullerene-like sphere 5 c is found for the first time. 相似文献
10.
《Tetrahedron letters》1988,29(49):6509-6512
The asymmetric synthesis of the α-pentyl succinate fragment of (-)-Actinonin is achieved using the chiral iron acetyl S-(+)-[(η5-C5H5)Fe(CO)(PPh3)COCH3] and subsequently converted to (-)-Actinonin in an overall yield of 41%. 相似文献
11.
12.
The Potential of the Diarsene Complex [(C5H5)2Mo2(CO)4(μ,η2-As2)] as a Connector Between Silver Ions
Dr. Mehdi Elsayed Moussa Jana Schiller Dr. Eugenia Peresypkina Dr. Michael Seidl Dr. Gábor Balázs Pavel Shelyganov Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14315-14319
The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(μ,η2-As2)] ( B ) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}3] (Ag[FAl]) and Ag[Al{OC(CF3)3}4] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η2- B )4Ag2][FAl]2 ( 4 ), [(μ,η1:η2- B )3(η2- B )2Ag3][TEF]3 ( 5 ) and [(μ,η1:η2- B )4Ag3][TEF]3 ( 6 ). These products are only composed of the complexes B and AgI. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [AgI]3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ-bond thus showing this unique feature of this diarsene ligand. 相似文献
13.
A. R. Kudinov A. A. Fil'chikov P. V. Petrovskii M. I. Rybinskaya 《Russian Chemical Bulletin》1999,48(7):1352-1355
The parent 30-electron triple-decker iron complex with cyclopentadienyl ligands, [(η-C5H5)Fe(μ-η:η-C5H5)Fe(η-C5H5)]PF6 (1), was prepared for the first time by visible-light irradiation of ferrocene and [(η-C5H5)Fe(η-C6H6)]PF6 in CH2Cl2 at 0 °C. An analogous reaction performed with the use of (η-C5H5)Co(η-C4Me4) (2) instead of ferrocene afforded the thermally labile 30-electron cationic iron-cobalt triple-decker complex [(η-C5H5)Fe(μ-η:η-C5H5)Co(η-C4Me4)]PF6. The latter reacted with compound 2 at 20 °C to form the symmetrical 30-electron cationic dicobalt triple-decker complex
[(η-C4Me4)Co(μ-η:η-C5H5)Co(η-C4Me4)] PF6.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 7, pp. 1364–1367, July, 1999. 相似文献
14.
《Journal of organometallic chemistry》1987,330(3):415-428
The crystal and molecular structures of (η5-C5H5)Fe[η5--C5H4CCo3(CO)9] (1), Pna21, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, Rw = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η5-C5H5Fe[η5--C5H4CCo3(η5C5H5)3CH] (2), P21/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and Rw = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo3 cluster core, while in 2 the CCo3C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents. 相似文献
15.
Anna Garbagnati Dr. Michael Seidl Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200669
The oxidation of [(Cp*Mo)2(μ,η6:η6-P6)] ( 1 ) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(Cp*Mo)2(μ,η3:η3-P3)(μ,η1:η1:η1:η1-P3I3)][X] (X=I3−, I−) ( 2 ) and [(Cp*Mo)2(μ,η4:η4-P4)(μ-PI2)][I3] ( 3 ), while the reaction with PBr5 led to the complexes [(Cp*Mo)2(μ,η3:η3-P3)(μ-Br)2][Cp*MoBr4] ( 4 ) [(Cp*MoBr)2(μ,η3:η3-P3)(μ,η1-P2Br3)] ( 5 ) and [(Cp*Mo)2(μ-PBr2)(μ-PHBr)(μ-Br)2] ( 6 ). The reaction of 1 with the far stronger oxidizing agent PCl5 was followed via time- and temperature-dependent 31P{1H} NMR spectroscopy. One of the first intermediates detected at 193 K was [(Cp*Mo)2(μ,η3:η3-P3)(μ-PCl2)2][PCl6] ( 8 ) which rearranges upon warming to [(Cp*Mo)2(μ-PCl2)2(μ-Cl)2] ( 9 ), [(Cp*MoCl)2(μ,η3:η3-P3)(μ-PCl2)] ( 10 ) and [(Cp*Mo)2(μ,η4:η4-P4)(μ-PCl2)][Cp*MoCl4] ( 11 ), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations. 相似文献
16.
17.
《Journal of organometallic chemistry》1995,503(2):C46-C47
The reaction of [Fe(CO)2(PPh3)2{η2-SCNC(O)Ph}] with [Co(η-C5H5)(PPh3)2] in benzene solution at room temperature results in the facile cleavage of the CS bond of the SCNC(O)Ph ligand to give [{Co(η-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S{μ3-CNC(O)Ph}], whereas [Fe(CO)2(PPh3)2(η2-SCNMe)] gives [{Co(η-C5H5)} 22{Fe(CO)(CNMe)(PPh3)(μ3-S)(μ3-CO)]. The structure of [{Co(η-C5H5)}2{Fe(CO)2(PPh3)} (μ3-CNC(O)Ph}] has been confirmed by X-ray diffraction. 相似文献
18.
《Journal of organometallic chemistry》1987,327(2):C41-C42
η-C5H5)Fe(CO)2 I reacts with pyrrole and indole in the presence of diisopropylamine, in sunlight, to give the corresponding (η-C5H5)Fe(CO)2-η1-N-heterocyclic complexes in 72–88% yield. 相似文献
19.
《Journal of organometallic chemistry》1987,331(3):357-377
The oxidative cleavage of [Fe2(η-C5H5)2(CO)4-n(CNMe)n] (n=0−2) by 2AgX gives mononuclear products. It is shown to be a two-electron process in most solvents but a one-electron process in acetonitrile. The two-electron oxidations proceed by way of adducts such as [Fe2(η-C5H5)2(CO)(CNMe)(μ-CO){;μ-CN(Me)AgPPh3};]BF4 which are isolable when n = 2, detectable when n = 1 and postulatetd when n = 0. The one-electron process gives no adducts, and 1AgX cleaves all of the substrate to [Fe(η-C5H5)(CO)(L)(NCMe)]+ and [Fe(η-C5H5)(CO)(L)]. (L CO or CNME). The latter may combine or react with added CHBr3 to give [Fe(η-C5H5)(CO)(L)Br]. The structure of [Fe(η-C5H5)(CO)2-(CNMe)]BF4 has been determined by X-ray diffraction. 相似文献
20.
A number of vanadocene complexes with asymmetrically substituted acetylenes, [Cp2V-(1-2η-R1C=CR2)] (R1 = Ph and SiMe2Ph; R2 = 4-biphenyl, 1-naphthyl, and Ge(CF3)3), were obtained and examined by ESR spectroscopy. The isotropic and anisotropic ESR spectra of the complexes containing the phenyl, biphenyl, naphthyl, or dimethyl(phenyl)silyl substituent in the alkyne ligand are typical of d1 complexes of vanadocene with alkynes. This is not the case of the complex containing the electron-withdrawing tris(trifluoromethyl)germyl group, whose isotropic and anisotropic ESR spectra show anomalous values of g factor and hyperfine coupling constant. 相似文献