- Polar cofacially fixed sandwich complexes: Do they demonstrate second harmonic generation (SHG)?
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For the purpose of possible second harmonic generation (SHG) a cationic and a neutral sandwich unit were cofacially arranged in a three-step synthesis starting from 1,8-diiodonaphthalene. First, 1-cyclopentadienyl-8-iodonaphthalene (2) was formed, then the neutral ferrocenyl substituent was fixed in the 8-position by a Negishi cross-coupling reaction. The deprotonation of the cyclopentadienyl substituent, and the subsequent coordination of the half-sandwich fragments ML = [Fe(η5-C5Me 5)]+, [Rh(η5-C5Me 5)]2+, [Ir(η5-C5Me 5)]2+, [Ru(η6-C6H 6)]2+ to the cyclopentadienyl anion revealed the desired dinuclear complexes 1-[(η5-cyclopentadienediyl)- (η5-pentamethylcyclopentadienyl)iron(II)]-8- ferrocenylnaphthalene (5), 1-[(η5-cyclopentadienediyl) (η5-pentamethylcyclopentadienyl)rhodium(III)]-8- ferrocenylnaphthalene hexafluorophosphate (6PF6), 1-[(η5-cyclopentadienediyl)(η5- pentamethylcyclopentadienyl)iridium(III)]-8-ferrocenylnaphthalene hexafluorophosphate (7PF6), and 1-[(η6-benzene) (η5-cyclopentadienediyl)ruthenium(II)]-8-ferrocenylnaphthalene hexafluorophosphate (8PF6). The neutral complex 5 was oxidized to the paramagnetic cation 1-[(η5-cyclopentadienediyl)- (η5-pentamethylcyclopentadienyl)iron(III)]-8- ferrocenylnaphthalene hexafluorophosphate (5PF6). Compounds 3, 5PF6, 6PF6, and 7PF6 were characterized by X-ray structure determination; the neutral compound 3 crystallizes in the space group P21/c, whereas all of the cationic dinuclear complexes crystallize in the chiral space group C2221. A cyclic voltammetry study points to a predominant through-space interaction between the cationic sandwich unit and the neutral ferrocene substituent. The compounds 5PF6, 6PF6, 7PF6, and 8PF6 were subjected to hyper-Rayleigh scattering (HRS) and Kurtz-powder measurements. In both studies no SHG intensity could be observed. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Malessa, Maik,Heck, Juergen,Kopf, Juergen,Garcia, M. Helena
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- Synthesis and reactions of ferrocenyl-capped long-chain alkynes
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Alkyl-substituted acetylenes and diacetylenes with terminal ferrocenyl groups were synthesised starting from ferrocene. The reactivity of the triple bonds in the resulting compounds was used to prepare cobalt-alkyne complexes. Cyclotrimerisation of the mo
- Bloemker, Tobias,Boeckmann, Philipp,Kehr, Gerald,Froehlich, Roland,Erker, Gerhard
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- Cyclopalladated complex of 1-ferrocenylisoquinoline
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A new dimeric cyclopalladated ferrocenyl complex di-μ -chloro-bis[2-(1-isoquinolinyl)ferrocenyl](C,N)dipalladium was obtained and characterized. Its catalytic properties in the Heck and Suzuki reactions (including a solid-phase version), as well as in hydroarylation of norbornene, were studied.
- Bulygina,Khrushcheva,Peregudov,Sokolov
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- TRIFERROCENYL-COMPLEXE VON WOLFRAM(VI): MOLEKUELSTRUKTUR IM FESTKOERPER UND DYNAMISCHES VERHALTEN IN LOESUNG VON TRIFERROCENYL-FERROCENOXY-OXO-WOLFRAM, WO(OFc)Fc3
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Triferrocenyltungsten complexes of the type WO(X)Fc3 (X=Cl, (1), OMe (2), OFc (3) and OnBu (4)) were obtained by treating WOCl4 with ferrocenyllithium, FcLi, in tetrahydrofuran solution.Reaction of WOCl4 with a threefold excess of FcLi gives 1, which may be converted into 2 using KOCH3.Reaction of WOCl4 with a sixfold excess of FcLi gives a mixture containing 3 und 4 in addition to ferrocene and biferrocene.According to the X-ray crystallographic analysis, WO(OFc)Fc3 (3) has a trigonal-bipyramidal structure with three ferrocenyl ligands occupying the equatorial positions and an axial ferrocenoxy group coordinated trans to the oxo ligand The three W-C(ferrocenyl) (average 2.092 angstroem) and the O-C(ferrocenyl) (1.33(1) angstroem) bond distances are remarkably short.The axial tungsten-oxygen distances correspond to a W=O double and a W-O single bond (1.705(5) and 1.945(5) angstroem), respectively.The 1H and 13C NMR spectra of WO(OFc)Fc3 (3) are temperature-dependent.This is ascribed to a hindered rotation of the ferrocenyl ligands around the W-C(ferrocenyl) bonds; the free activation enthalpy ΔG(excit.)(Tc) of this intramolecular dynamic process is 62.5 +/- 0.5 kJ mol-1.
- Herberhold, Max,Kniesel, Heidemarie,Haumaier, Ludwig,Thewalt, Ulf
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- Bis(ferrocenylsilyl)thiophenes and ferrocenylene(silylene) thiophene oligomers
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The reaction between 1,1'-dilithioferrocene and 2,5-bis (chlorodimethylsilyl) thiophene (I), leads to a series of cyclic oligomers of basic formulation [Fc-SiMe2-TH-SiMe2](n) (II); Fc = (η5-C5H4)2Fe, TH = C4H2S. The material n = 2, IIa, has been completely characterized by spectroscopic and single crystal X-ray diffraction. Cyclic voltammetric analysis of IIa illustrates two reversible redox processes, indicating a significant interaction between the two ferrocenylene units despite the 5 atom bridge. By comparison, the monomeric analog Fc-SiMe2-TH-SiMe2-Fc (III), Fc = (η5-C5H5)Fe(η5-C5H4), prepared from the reaction of mono-lithioferrocene with I, exhibits a single redox process, even though there is the same bridge between the two Fe centers. (C) 2000 Elsevier Science Ltd.
- Pannell,Wang,Sharma,Cervantes-Lee
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- Ferrocene-containing sterically hindered phosphonium salts
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The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations b
- Ermolaev, Vadim,Gerasimova, Tatiana,Kadyrgulova, Liliya,Shekurov, Ruslan,Dolengovski, Egor,Kononov, Aleksandr,Miluykov, Vasily,Sinyashin, Oleg,Katsyuba, Sergei,Budnikova, Yulia,Khrizanforov, Mikhail
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- Synthesis, Aromaticity and Photophysical Behaviour of Ferrocene- and Ruthenocene-Appended Semisynthetic Chlorin Derivatives
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Two novel synthetic strategies to covalently link a metallocene electron-donor unit to a chlorin ring are presented. In one approach, pyropheophorbide a is readily converted into its 131-ferrocenyl dehydro derivative by nucleophilic addition of
- Nikkonen, Taru,Moreno Oliva, Mara,Taubert, Stefan,Melchionna, Michele,Kahnt, Axel,Helaja, Juho
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- Untersuchungen zur Darstellung und Reaktivitaet von Triferrocenylwolfram(VI)-Komplexen
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A series of mononuclear triferrocenyltungsten(VI) complexes of the type WO(X)Fc3 (X=Cl, F; OMe, OEt, OnBu, OtBu, OFc) which are accessible by reaction of WOCl4 with an excess of ferrocenyllithium, FcLi, is described.A binuclear, oxo-bridged complex 2(μ-O) has also been isolated.The new compounds have been characterized on the basis of their mass spectra and their (temperature-dependent) 1H and 13C(1H) NMR spectra.
- Herberhold, Max,Kniesel, Heidemarie
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- Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si-O-CHCH2 and Si-(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments
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The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc2(CH3)3C(CH2)2SiCHCH2 (5), Fc2(CH2CH-O)SiCHCH2 (6), Fc2(OH)SiCHCH2 (7), Fc2(CH2CH-O)Si-O-Si(O-CHCH2)Fc2 (8) and Fc2(CH2CH-O)Si-O-SiFc3 (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH2CH-OLi or (CH3)3C(CH2)2Li with the corresponding multifunctional chlorosilane, Cl3SiCHCH2 or Cl3Si-O-SiCl3. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different CC polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF6]- to [B(C6F5)4]-, the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.
- Bru?a, Sonia,González-Vadillo, Ana M.,Ferrández, Marta,Perles, Josefina,Montero-Campillo, M. Merced,Mó, Otilia,Cuadrado, Isabel
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- Rhodium(I) and Iridium(I) Complexes of Ferrocenyl-Functionalized Amidinates and Bis(amidinates): κ2 N-Coordination Versus Ferrocenyl Ortho-Metalation
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The synthesis and characterization of two bulky ferrocenyl-functionalized amidinates and their lithium, potassium, rhodium(I), and iridium(I) complexes are reported. The ferrocenyl mono(amidine) [Fc{C(NDipp)(NHDipp)}] (1) (Fc = ferrocenyl; Dipp = 2,6-diisopropylphenyl) and its potassium complex [Fc{C(NDipp)2K}·3THF] (2) as well as the 1,1′-ferrocendiyl-bridged bis(amidinate) [fc{C(NMes)2Li}2·3THF] (3) (fc = ferrocene-1,1′-diyl; Mes = mesityl) were synthesized. Salt metathesis reactions with the metal precursors [Rh(cod)Cl]2 (cod = 1,5-cyclooctadiene) and [Ir(cod)Cl]2 gave the rhodium(I) and iridium(I) complexes [Fc{C(NDipp)2Rh(cod)}] (4), [fc{C(NMes)2Rh(cod)}2] (5), and [fc{C(NMes)2Ir(cod)}2] (6), as well as the ortho-metalated compound [(Cp)Fe(C5H3){C(NHDipp)(NDipp)Ir(cod)}] (7). As complex 7 showed an ortho-metalation on the ferrocene backbone, we investigated this reaction in more detail. It was found that the rhodium(I) complexes 4 and 5 also undergo ortho-metalation upon treatment with carbon monoxide (CO). After the carbonylation, the first known ortho-metalation of rhodium(I) on ferrocene complexes was observed for [(Cp)Fe{(C5H3)C(NHDipp)(NDipp)Rh(CO)2}] (8) and [Fe(C5H3)2{C(NHMes)(NMes)Rh(CO)2}2] (9). A combined electrochemical and quantum chemical study revealed that depending on both the metal-bound ligand (CO vs cod) and the bonding mode (κ2N vs ortho-metalated), the highest occupied molecular orbital is located more on iron or on rhodium/iridium.
- Kaufmann, Sebastian,Radius, Michael,Moos, Eric,Breher, Frank,Roesky, Peter W.
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- Ruthenium complexes of: P -stereogenic phosphines with a heterocyclic substituent
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The synthesis via phosphine-boranes of 13 new optically pure P-stereogenic diarylphosphines P(Het)PhR (Het = 4-dibenzofuranyl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl-S,S-dioxide (DBTO2) and 1-thianthrenyl (TA); R = OMe, Me, i-Pr, Fc (ferrocenyl)) following the Jugé-Stephan method is described. The ligands were designed with the aim of having a heteroatom in a position capable of interacting with a metal upon coordination. The ligands and their precursors have been fully characterised, including the determination of two crystal structures of phosphine-boranes. Ru neutral complexes of the type [RuCl2(η6-arene)(κP-P)] (arene = p-cymene and methyl benzoate) have been prepared and characterised, including three crystal structure determinations. Treatment of solutions of the complexes with TlPF6 allowed the preparation of well-defined cationic complexes [RuCl(η6-arene)(κ2P,S-P)]PF6 for DBT- and TA-based phosphines. The complexes possess a stereogenic Ru atom and in most of the cases they are present as a single isomer in solution. All the Ru complexes have been used in the asymmetric transfer hydrogenation of acetophenone in refluxing 2-propanol, with good activities and up to 70% ee.
- Clavero, Pau,Grabulosa, Arnald,Rocamora, Mercè,Muller, Guillermo,Font-Bardia, Mercè
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- The Crystal Structure of the THF Adduct of Monolithioferrocene
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Single crystals of [Fe(η5-C5H4)(η5-C5H5)]2Li2(thf)4 (1) were obtained from a tetrahydrofuran solution containing monolithioferrocene. The title compound crystallizes in the monoclinic space group P21 with a = 9.6589(5) ?, b = 17.4285(9) ?, c = 30.3116(15) ?, β = 91.911(2)° and V = 5099.8(5) ?3 with three independent molecules of 1. All individual molecules feature a non- symmetric almost planar Li2C2 four-membered ring with two shorter (2.118-2.215 ?) and two longer Li-C distances (2.257-2.309 ?). The lithium cations are each coordinated by two carbanionic atoms of two ferrocenyl substituents and two tetrahydrofuran molecules in a distorted tetrahedral fashion. All ferrocenyl moieties display an eclipsed conformation of the C5 rings.
- F?rster, Christoph,Heinze, Katja
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- Synthetic, redox and coordination chemistry of bis(pentachlorophenyl)boryl ferrocene, FcB(C6Cl5)2
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Two synthetic approaches to bis(pentachlorophenyl)boryl ferrocene have been explored. One mirrors that used in a novel approach to FcB(C6F 5)2 from FcBBr2, but is less selective than its perfluorinated counterpart on account of the greater steric bulk of LiC 6Cl5 over LiC6F5. This approach does, however, provide a viable route to unsymmetrical mono(pentachlorophenyl) derivatives of the type FcB(C6Cl5)Ar through the intermediacy of the mono-substituted species FcB(C6Cl5)Br. FcB(C6Cl5)2 itself is best synthesized from ferrocenyllithum and ClB(C6Cl5)2 and is a violet-blue species featuring an extremely electron deficient Fe(II) centre (E1/2 = +550 mV with respect to ferrocene/ferrocenium). A combination of structural, spectroscopic and reactivity studies of these and related ferrocenylboranes allow some general comments to be made concerning the relative steric and electronic properties of the C6Cl5 group. Thus, in terms of their relative capabilities as electron-withdrawing groups the substituents examined can be ranked C6Cl5 > C 6F5 > Mes, while steric properties are ordered Mes > C6Cl5 > C6F5.
- Kelly, Michael J.,Tirfoin, Remi,Gilbert, Jessica,Aldridge, Simon
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- Diphosphines and Metal Complexes
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Compounds of the formula I or I′, where the radicals R1 are each, independently of one another, a hydrogen atom or C1-C4-alkyl and R′1, is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; R2 is hydrogen, R01R02R03Si— is halogen-, hydroxyl-, C1-C8-alkoxy- or R04R05N-substituted C1-C18-acyl or is R06—X01—C(O)—; R01, R02 and R03 are each, independently of one another, C1-C12-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C6-C10-aryl or C7-C12-aralkyl; R04 and R05 are each, independently of one another, hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl, or R04 and R05 together are trimethylene, tetramethylene, pentamethylene or 3-oxapentylene; R06 is C1-C18-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl; X01 is —O— or —NH—; T is C-bonded C3-C20-heteroarylene; v is 0 or an integer from 1 to 4; X1 in the heteroring of the heteroarylene is bound in the ortho position relative to the T—C* bond; and * indicates a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically pure diastereomers. The compounds are excellent chiral ligands for metal complexes as enantioselective catalysts for the hydrogenation of prochiral organic compounds.
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(2009/10/31)
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- METHOD FOR PRODUCING ORTHOMETALATED AND ORTHOSUBSTITUTED AROMATIC COMPOUNDS
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The invention relates to compounds having a structural element of formula (I) in an aromatic hydrocarbon ring, wherein: M represents -Li, -MgX3, (C1-C18-Alkyl)3Sn-, -ZnX3 or -B(O-C1-C4-Alkyl)2; X1 and X2, independent of one another, represent O or N, and C-bound hydrocarbon radicals or heterohydrocarbon radicals are bound to the free bonds of the O and N atoms; group -C=C-, together with C atoms, forms a hydrocarbon aromatic compound and represents X3 Cl, Br or I. The inventive compounds are easily obtained by directly substituting the hydrogen in the ortho position to the P atom with metalation reagents. The metal atoms can then be substituted by a reactive electrophilic compound. The group -P(X1-)(X2-)----(BH3)0,1 can then be converted into a secondary phosphine group. The inventive method enables the production of monophosphines and diphosphines even on a large scale, which are valuable ligands for metal complexes serving as catalysts for, e.g. enantioselective hydrogenations.
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(2008/06/13)
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- A direct meta-lithiation route to 1,3-disubstituted ferrocenes
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Ferrocenyl sulfides afford meta-lithiation products with up to 94% regioselectivity on reaction with s-BuLi; the resulting 1,3-disubstituted ferrocenes can then be reacted with a variety of electrophiles.
- Pichon, Christophe,Odell, Barbara,Brown, John M.
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p. 598 - 599
(2007/10/03)
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- Synthesis, structural characterization and 57Fe-M?ssbauer spectra of ferrocenylhexasilanes
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Linear and cyclic ferrocenylhexasilanes 1,6-Fc-Si6Me12-X [X=Me, -C6H4CH=C(CN)2], 1,3- and 1,4-Fc-Si6Me10-X [X=Me, -C6H4CH=C(CN)2], have been synthesized and their M?ssbauer spectra have been measured. All compounds possess localized electronic structures on the M?ssbauer timescale and partial Fe(III) character of the iron atom due to Cp→(Sin) electron transfer. The M?ssbauer data obtained, furthermore, indicate considerable aryl-ferrocenyl interaction via the hexasilane moiety. The single crystal X-ray structures of 1,3- and 1,4-Fc-Si6Me10-C6H4CH=C(CN) 2 exhibit the cyclohexasilane ring in chair conformation with the bulky Fc- and aryl substituents in equatorial positions.
- Rautz, Hermann,Stüger, Harald,Kickelbick, Guido,Pietzsch, Claus
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p. 167 - 178
(2007/10/03)
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- Synthesis, Spectroscopy, Electrochemical Characterization, and Nonlinear Optical Properties of Ferrocenyloligosilanes: FcSinMe2n(C6H5) (n = 1-6) and FcSi2Me4(C6H4-X) (
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New ferrocenyloligosilylene aryl complexes have been synthesized, FcSinMe2nC6H5 (n = 1-6) and FcSi2Me4{C6H4-X} (X = m-CF3· p-Cl, p-Br, p-OMe, p-NMe2/s
- Sharma, Hemant K.,Pannell, Keith H.,Ledoux, Isabelle,Zyss, Joseph,Ceccanti, Antonio,Zanello, Piero
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p. 770 - 774
(2008/10/08)
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- N,N'-diferrocenyl-N-heterocyclic carbenes and their derivatives
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In continuation of our work on Wanzlick/Arduengo carbenes containing redox-active ferrocenyl substituants we report on the synthesis of N,N'-diferrocenyl imidazol(in)ium salts as precursors of imidazol(in)-2-ylidenes. The necessary starting material for t
- Bildstein, Benno,Malaun, Michael,Kopacka, Holger,Wurst, Klaus,Mitterb?ck, Martin,Ongania, Karl-Hans,Opromolla, Giuliana,Zanello, Piero
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p. 4325 - 4336
(2008/10/08)
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- Ferrocene Derivatives of Squaric Acid and Propiolic Acid. Syntheses and Reactions
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Concepts for linking ferrocene derivatives with conjugated squarate and propiolate based spacer systems have been investigated.Coupling of 3,4-dichlorocyclobut-3-ene-1,2-dione (squaric acid dichloride) with cuproferrocene dimethylsulfide resulted in 3-chloro-4-ferrocenylcyclobut-3-ene-1,2-dione (ferrocenylsemisquaric acid chloride) and 3,4-diferrocenylcyclobut-3-ene-1,2-dione.Ferrocenylsemisquaric acid chloride was further treated with ethynylferrocene and 4-ethynyl-4-(ferrocenylethynyl)tolan, respectively, to form the corresponding mixed squaric diketones, which required Zn/Pd mediated coupling conditions for sufficient conversion.The symmetrically substituted derivative of ferrocenylacetylene was prepared by the same method.Cupration and subsequent coupling of dilithioferrocene with one equivalent of iodopropiolic acid methyl ester yielded 1'-iodo-1-ferrocenylpropiolic acid methyl ester, and with two equivalents 1,16-bis(methoxycarbonylethynyl)biferrocene.Nucleophilic addition of secondary amines to ferrocenylpropiolic acid ethyl ester gave aminoacrylates as intermediates, which rapidly converted to ketoesters during workup.Only in the case of morpholine the corresponding adduct (ferrocenylmorpholino acrylate) could be isolated. 1,3-Diferrocenylprop-2-ene-1-one has been obtained in a Benary reaction of lithioferrocene with 3-diethylaminoethyl acrylate in quantitative yield.In order to provide alternative syntheses of already known compounds the substitution behavior of different metallated ferrocene intermediates has also been evaluated by reaction with other acid halides (oxalyl chloride, thiophosgene, ethyl chloroformate).All new compounds, 3-chloro-4-ferrocenylcyclobut-3-ene-1,2-dione (1);3,4-diferrocenylcyclobut-3-ene-1,2-dione (2); 3,4-diferrocenylethynylcyclobut-3-ene-1,2-dione (3); 3-ferrocenyl-4-ferrocenylethynylcyclobut-3-ene-1,2-dione (4); 3-ferrocenyl-4-ferrocenylethynylphenylethynylphenylethynylcyclobut-3-ene-1,2-dione (5); 3-(N-morpholino)-3-ferrocenylethyl acrylate (6); 3-ferrocenyl-3-ketoethyl propanoate (7); iodoferrocenylpropargylic acid methyl ester (8); 1,16-bis(methoxycarbonylethynyl)biferrocene (9) and trans-1,3-diferrocenylprop-2-ene-1-one , have been characterized by IR, MS and NMR and in several cases by UV/VIS and DSC.Key words: Ferrocenes, Alkynes, Squaric Acid Derivatives, Propiolic and Acrylic Esters
- Schottenberger, Herwig,Buchmeiser, Michael,Polin, Johann,Schwarzhans, Karl-Eberhard
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p. 1524 - 1532
(2007/10/02)
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- Tin(IV) Compounds Containing Ferrocenyl Chalcogenate and Ferrocenylene Dichalcogenate Ligands. Synthesis ans Multinuclear NMR Soectroscopy
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A series of tin(IV) compounds containing ferrocenyl chalcogenates (FcE) and ferrocenylene dichalcogenate (fcE2) ligands (E = S, Se, Te) has been synthesized for a systematic study of the NMR spectra with particular emphasis on (13)C, (119)Sn, (77)Se and (125)Te NMR.All compounds are formally derived from tetramethylstannane, SnMe4, by stepwise replacement of methyl by either FcE or fcE2 ligands.Starting from lithioferrocene the products are tetrasubstituted stannanes Me4-nSn(EFc)n (n = 1 and 2, E = S, Se, Te; n = 3 and 4, E = S, Se).Starting from 1,1'-dilithioferoocene, the products are 1,1'-disubstituted ferrocenes such as fc(E-SnMe3)2 (E = S, Se, Te), although 1,3-dichalcogenaferrocenophane rings are formed whenever possible to give ferrocenophanes fcE2SnMe2 (E = S, Se, Te) and fc2 (E = S, Se) or tin spiro compounds Sn(E2fc)2 (E = S, Se, Te).Whereas all (8) possible sulfur-containing and all (8) selenium-containing products were accessible, some of the tellurium-rich compounds could not be isolated due to preferred formation of either Fc2Te or fcTe3.All compounds were characterized on the basis of their (1)H, (13)C, (119)Sn and, if possible, (77)Se and (125)Te solution NMR spectra.In many cases, coupling constants such as 2J((119)Sn(1)H), nJ((119)Sn(13)C), (n = 1,2,3), 1J((119)Sn(77)Se) and 1J((125)Te(119)Sn), 1J((77)Se(13)C) and 1J((125)Te(13)C) could be determined.The δ(119)Sn chemical shifts of analogous phenyl and ferrocenyl compounds, Me4-nSn(EPh)n and Me4-nSn(EFc)n (n = 0-4, E = S, Se, Te) are discussed, and for a microcrystalline sample of tetrakis(ferrocenylselenato)stannane, Sn(SeFc)4, the (119)Sn and (77)Se CP/MAS NMR spectra are reported and compared with the solution spectra. Key words: Tin(IV) chalcogenates; ferrocenyl chalcogenates; ferrocenophanes; NMR spectra.
- Herberhold, Max,Huebner, Michaela,Wrackmeyer, Bernd
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p. 940 - 950
(2007/10/02)
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- The synthesis of dipridyl- and 1,10-phenanthrolylferrocenes and bis-N,N'-(2,2'-dipyridyl(6-ferrocenyl-N,N'-2,2'-dipyridyl)ruthenium dichloride
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Ferrocenyldipyridyls and ferrocenyl-o-phenanthrolines have been synthesized by the direct reaction of lithioferrocenes with the appropriate dipyridine or 1,10-phenanthroline.The spectroscopic properties of these potential new ligands are described and the synthesis of bis-2,2'-dipyridyl(6-ferrocenyl-2,2'-dipyridyl)ruthenium dichloride, 8, in its hydrated from is reported.
- Butler, Ian R.,Roustan, Jean-Louis
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p. 2212 - 2215
(2007/10/02)
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- ?-Ferrocenyl Complexes of the Early Transition Metals - Synthesis and Structure
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Ferrocenyllithium, FcLi (1), reacts with (C5H4CH3)2TiCl2, CpTiCl3 and Cp*TiCl3 to give the new ?-ferrocenyl complexes (C5H4CH3)2TiFc2 (2), CpTiFc3 (3) and Cp*Ti(Fc)2Cl (4), respectively.Treatment of Cp*2ZrCl2 with FcLi yields the mono-substitution product Cp*2Zr(Fc)Cl (5), which has been characterized by an X-ray structure analysis.Compound 5 crystallizes in the monoclinic space group P21/c (a = 1622.3(6), b = 995.0(2), c = 1664.3(6) pm; β = 94.78(3) deg; Z = 4).Due to the sterically demanding pentamethylcyclopentadienyl ligands 5 contains a long zirconium-carbon bond (231.4(8) pm) and the Cp rings of the ferrocenyl substituent are tilted by 10.2 deg.The syntheses of CpZrFc3 (6), Cp*HfFc3 (7) and Cp2VFc2 (8) are also described. - Keywords: Ferrocene, Early Transition Metals, Crystal Structure
- Wedler, Michael,Roesky, Herbert W.,Edelmann, Frank T.,Behrens, Ulrich
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p. 1461 - 1467
(2007/10/02)
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- Ferrocenylchalkogenide
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The very first examples of ferrocenyltellurium compounds are described.Insertion of tellurium into ferrocenyllithium led to an intermediate , which, upon oxidation in air, gave diferrocenylditelluride, Te2Fc2, in 50percent yield.The reaction of Te
- Herberhold, Max,Leitner, Peter
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p. 153 - 162
(2007/10/02)
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- Synthese und Reaktivitaet von Ferrocenyl-Pentacarbonylmangan, Mn(CO)5Fc
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The compound Mn(CO)5Fc can be prepared by the reaction of Mn(CO)5Br with ferrocenyllithium, FcLi.The mangana-β-diketone H, obtained as a side-product, is converted into Mn(CO)5Fc with concomitant formation of diferrocenoyl, (FcCO)2.In prot
- Herberhold, Max,Kniesel, Heidemarie
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p. 347 - 358
(2007/10/02)
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- Synthesis of new biferrocene derivatives containing interannular bridges and their mixed-valence analogues
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A series of biferrocene (Fc-Fc) (1) related compounds consisting of the coupled bridged ferrocenes [3]Fc-Fc (2), [3]Fc-[3]Fc (3), [4]Fc-Fc (4), [4]Fc-[4]Fc (6), and [4]Fc-[3]Fc (5) (Fc = ferrocene and [n]Fc = [n]-ferrocenophane) has been synthesized, and intervalence electron transfer in their mixed-valence cations has been investigated. The dimers 3 and 6 are prepared by Ullmann coupling of 3-I-[3]Fc (11) and 3-I-[4]Fc (12), respectively. The unsymmetrical compounds 2 and 4 are synthesized by the cross-coupling of the above iodo derivatives with ferrocenylzinc chloride using PdCl2(dppf) as catalyst. The same catalyst is used to couple 12 with 3-ZnCl-[3]Fc to give 5. Synthesis of the iodo precursors 11 and 12 is also described. Cyclic voltammetry of compounds 1-6 in CH3CN shows two reversible one-electron processes for each of the coupled compounds. Mixed-valence ions of 1-6 are prepared by controlled current oxidation, and the intervalence-transfer bands in the near-IR are reported.
- Talham, Daniel R.,Cowan, Dwaine O.
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p. 932 - 937
(2008/10/08)
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- A HIGH YIELD SYNTHESIS OF BIFERROCENYL
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Biferrocenyl has been obtained in 78percent yield by reaction of monolithioferrocene with p-xylene dibromide.
- Koray, Ali R.,Ertas, Muemtaz,Bekaroglu, Oezer
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