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1.
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
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Stephan Reichl Christoph Riesinger Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2023,62(36):e202307696
By the reaction of [Cp*Fe(η5-As5)] ( I ) (Cp*=C5Me5) with main group nucleophiles, unique functionalized products with η4-coordinated polyarsenide (Asn) units (n=5, 6, 20) are obtained. With carbon-based nucleophiles such as MeLi or KBn (Bn=CH2Ph), the anionic organo-substituted polyarsenide complexes, [Li(2.2.2-cryptand)][Cp*Fe(η4-As5Me)] ( 1 a ) and [K(2.2.2-cryptand)][Cp*Fe{η4-As5(CH2Ph)}] ( 1 b ), are accessible. The use of KAsPh2 leads to a selective and controlled extension of the As5 unit and the formation of the monoanionic compound [K(2.2.2-cryptand][Cp*Fe(η4-As6Ph2)] ( 2 ). When I is reacted with [M]As(SiMe3)2 (M=Li ⋅ THF; K), the formation of the largest known anionic polyarsenide unit in [M′(2.2.2-cryptand)]2[(Cp*Fe)4{μ5-η4:η4:η3:η3:η1:η1-As20}] ( 3 ) occurred (M′=Li ( 3 a ), K ( 3 b )). 相似文献
4.
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
5.
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
6.
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
7.
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
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《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
9.
Vladimir I. Bakhmutov Aida Contreras-Ramirez Hannah Drake Hong-Cai Zhou 《Magnetic resonance in chemistry : MRC》2022,60(6):541-553
Solid-state NMR experiments on 2H, 31P, 13C, and 1H nuclei, including 31P T1, 1H T1, and 1H T1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D2O and/or CD3OD. The 13C{1H} CP MAS NMR experiment performed for compound 1-CD 3 OD (Zr (HPO4)2 . 0.2CD3OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD3 rotations around the C3-axis. It has been demonstrated that the intercalated species, D2O and CD3OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems. 相似文献
10.
《Journal of organometallic chemistry》1992,430(1):C10-C14
The lone-pair electrons of one of the two directly bonded phosphorus atoms of the P3C2tBu2 ring in the penta- or hexaphosphaferrocene complexes [Fe(η5-P3C2tBu2)(η5-P3C2tBu3)] and [Fe(η5P3 C2tBu2)2] can ligate to other metal centres to afford novel bi- and tetrametallic complexes, whose structures have been elucidated by NMR and single crystal X-ray crystallographic studies. 相似文献
11.
《Journal of organometallic chemistry》1989,373(2):C17-C20
The synthesis of the novel “slipped” sandwich compound [Ni(η5-P3C2R2)(η3-P2C3R3)] (R = But) is described. The mode of attachment of the P3C2R2 and P2C3R3 rings has been determined by NMR spectroscopy and a single crystal X-ray diffraction study. 相似文献
12.
S. A. Sapchenko D. G. Samsonenko V. P. Fedin I. Boldog K. V. Domasevich 《Russian Journal of Coordination Chemistry》2011,37(2):100-106
Crystals of a new coordination polymer with the framework structure, [Zn2(DMA)(Atc)] · DMA (I), were prepared by heating a solution of Zn(NO3)2 · 6H2O and H4Atc (H4Atc is 1,3,5,7-adamantanetetracarboxylic acid) in N,N′-dimethylacetamide (DMA). Colorless crystals of Zn2(Atc) · 2MeOH · 4H2O (II) were obtained by soaking the crystals of compound I in methanol. The structure of compound I was determined by X-ray diffraction analysis. Compounds I and II were characterized by X-ray powder diffraction, IR spectroscopy, thermal gravimetric analysis, and elemental analysis. The luminescence properties of compound I were studied. 相似文献
13.
The reaction of [(η-C7H7)Mo(MeCN)3)]BF4 with (η-C5Me5)Fe(η-P5) afforded the new 30-electron triple-decker complex [(η-C7H7)Mo(μ-η:η-P5)Fe(η-C5Me5)]BF4. Studies of the temperature dependence of the1H NMR spectra demonstrated that the resulting compound contains a fluxional cyclohepatrienyl ligand.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1374–1376, July, 1999. 相似文献
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《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
17.
Braunschweig H Fuss M Kupfer T Radacki K 《Journal of the American Chemical Society》2011,133(15):5780-5783
Selective dimetalation of a sandwich complex featuring the cyclooctatetraene ligand has been accomplished for the first time. The isolation of the dilithiated species 1 subsequently enabled the isolation of a paramagnetic [2]stannatitanoarenophane (2) via salt elimination reaction. Chemical oxidation resulted in the formation of a rare example of a cationic ansa-complex (3). 相似文献
18.
Piero Zanello Rolfe H. Herber Alexander R. Kudinov Maddalena Corsini Fabrizia Fabrizi de Biani Israel Nowik Dmitry A. Loginov Mikhail M. Vinogradov Lidia S. Shul’pina Igor A. Ivanov Anna V. Vologzhanina 《Journal of organometallic chemistry》2009,694(7-8):1161-1171
Visible light irradiation of cation [(η5-C6H7)Fe(η-C6H6)]+ (1+) in acetonitrile results in substitution of the benzene ligand giving the labile acetonitrile derivative [(η5-C6H7)Fe(MeCN)3]+ (2a+). The stable isonitrile and phosphite complexes [(η5-C6H7)FeL3]+ [L = tBuNC (2b+), P(OMe)3 (2c+), P(OEt)3 (2d+)] were obtained by reaction of 1 with L in MeCN. The structures of 2cPF6, [CpFe(η-C6H6)]PF6 (3PF6), and Cp1Fe(η-C6H6)]PF6 (4PF6) were determined by X-ray diffraction.The redox activity of the cyclohexadienyl complexes 1+, 2b+?2d+ has been investigated by electrochemical techniques and compared with that of the related cyclopentadienyl complexes 3+ and 4+. DFT calculations of the redox potentials and the respective geometrical changes were performed.Variable temperature Mössbauer (ME) spectroscopy has elucidated the relationship between structure and formal oxidation state of the iron atom in these complexes. In the case of 3+ an unexpected pair of crystallographic changes has been observed and interpreted in terms of both a second and first order phase transition. The mean-square-amplitude-of-vibration of the metal atom has been compared between the ME and X-ray data. ME measurements in a magnetic field have shown that in 4+ the quadrupole splitting is positive as it is in ferrocene. 相似文献
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M. Frauenkron N. Tzavellas N. Klouras C. P. Raptopoulou 《Monatshefte für Chemie / Chemical Monthly》1996,127(11):1137-1143
Summary A series of new compounds with molecular formula [Ti(5-C5H5)Cl2(OR)] (R=C6H11 (cyclohexyl,1), CH2CH(CH3)2 (2), CH(C2H5)2 (3), and CH2C6H5 (4)) has been obtained by the reaction of [Ti(5-C5H5)Cl3] with the appropriate alcohol. All complexes were characterized by elemental analysis and by IR and1H NMR spectroscopy. The structure of1 was determined by X-ray diffraction studies; crystal data: triclinic,a=11.334(2),b=13.590(2),c=12.237(2) Å, =113.501(5), =118.182(5), =101.993(6),V=1328.2(4) Å3,T=298K, space P1,Z=4, two crystallographically independent molecules in the unit cell. FinalR andR
w values are 0.0583 and 0.0632, respectively. Compound1 exhibits surprisingly short Ti-Cl and Ti-O distances, suggesting strong donation by the chloride and in particular by the alkoxide ligand. The Ti-O-C angle is unusually large.
Neue [Ti(5-C5H5)Cl2(OR)]-Komplexe. Kristall- und Molekülstruktur von 5-Cyclopentadienyl(cyclohexoxy)titan(IV) Dichlorid
Zusammenfassung Durch Umsetzung von [Ti(5-C5H5)Cl3] mit dem geeigneten Alkohol wurde eine Reihe von neuen Verbindungen der Formel [Ti(5-C5H5)(OR)] (R=C6H11 (cyclohexyl,1), CH2CH(CH3)2 (2), CH(C2H5)2 (3) und CH2C6H5 (4)) erhalten. Alle Komplexe wurden elementaranalytisch sowie IR- und1H-NMR-spektroskopisch charakterisiert. Die Struktur von1 wurde röntgenographisch bestimmt; Kristalldaten: triklin,a=11.334(2),b=13.590(2),c=12.237(2) Å, =113.501(5), =118.182(5), =101.993(6),V=1328.2(4) Å3,T=298K, Raumgruppe P1,Z=4, zwei kristallographisch unabhängige Moleküle in der Elementarzelle; abschließendeR-Werte:R=0.0583 undR w=0.0632. Verbindung1 zeigt überraschend kurze Ti-Cl- und Ti-O-Abstände; dies deutet auf eine starke -Elektronendonorwirkung des Chlorid- und vor allem des Alkoxidliganden hin. Der Ti-O-C-Bindungswinkel ist ungewöhnlich groß.相似文献
20.
Flambard A Köhler FH Lescouëzec R Revel B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(41):11567-11575
Magic-angle spinning (MAS) NMR spectroscopy is used to study the local structure and spin delocalisation in Prussian blue analogues (PBAs). We selected two common archetypes of PBAs (A(I)M(II)[M(III)(CN)(6)]·xH(2)O and M(II)(3)[M(III)(CN)(6)](2)·xH(2)O, in which A(I) is an alkali ion, and M(II) and M(III) are transition-metal ions) that exhibit similar cubic frameworks but different microscopic structures. Whereas the first type of PBA contains interstitial alkali ions and does not exhibit any [M(III)(CN)(6)](3-) vacancies, the second type of PBA exhibits [M(III)(CN)(6)](3-) vacancies, but does not contain inserted alkali ions. In this study, we selected Cd(II) as a divalent metal in order to use the (113)Cd nuclei (I=1/2) as a probe of the local structure. Here, we present a complete MAS NMR study on two series of PBAs of the formulas Cd(II)(3)[Fe(III)(x)Co(III)(1-x)(CN)(6)](2)·15H(2)O with x=0 (1), 0.25 (2), 0.5 (3), 0.75 (4) and 1 (5), and CsCd(II)[Fe(III)(x)Co(III)(1-x)(CN)(6)]·0.5H(2)O with x=0 (6), 0.25 (7), 0.5 (8), 0.75 (9) and 1 (10). Interestingly, the presence of Fe(III) magnetic centres in the vicinity of the cadmium sites has a magnifying-glass effect on the NMR spectrum: it induces a striking signal spread such that the resolution is notably improved compared to that achieved for the diamagnetic PBAs. By doping the sample with varying amounts of diamagnetic Co(III) and comparing the NMR spectra of both types of PBAs, we have been able to give a view of the structure which is complementary to that usually obtained from X-ray diffraction studies. In particular, this study has shown that the vacancies are not randomly distributed in the mesoporous PBAs. Moreover the cadmium chemical shift, which is a measure of the hyperfine coupling, allows the estimation of the spin density on the cadmium nucleus, and consequently, the elucidation of the spin delocalisation mechanism in these compounds along with its dependency on structural parameters. 相似文献