Ferrocenylalkynes as ligands in transition metal complexes

Champeil, Élise; Draper, Sylvia M.

doi:10.1039/b008803j

Cited by 28 publications

(14 citation statements)

References 30 publications

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“…In contrast, the acetylenic proton of 10 experiences a drastic shift of ca. 3.6 ppm towards lower field and is recorded at δ = 6.31 ppm in the cobalt complex 24 , similar to the analogous ferrocene compound 19. In addition, the IR data of 24 and 25 also closely resemble those of the ferrocene analogue.…”

Section: Resultssupporting

confidence: 55%

“…3.6 ppm towards lower field and is recorded at δ = 6.31 ppm in the cobalt complex 24, similar to the analogous ferrocene compound. [19] In addition, the IR data of 24 and 25 also closely resemble those of the ferrocene analogue. Crystals of 25 were obtained by slowly cooling a hexane solution and investigated by X-ray diffraction.…”

Section: Carbonylcobalt Complexesmentioning

confidence: 65%

“…Concerning the (CO) 6 Co 2 C 2 core, the bond lengths are within the range usually observed for compounds of this type and closely resemble those in related ferrocene compounds in particular. [19,20] For example, the bond length in the acetylenic CC fragment is 1.334(7) Å, whereas that for the Co-Co bond is 2.4697(11) Å. The C-Co distances are in the range 1.963(5)-2.013(5) Å.…”

Section: Carbonylcobalt Complexesmentioning

confidence: 99%

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Unsaturated Organic Derivatives of Phosphaferrocene – Synthesis and Reactivity of Vinyl‐ and Alkynylphosphaferrocenes

2012

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Starting from 2-formyl-3,4-dimethylphosphaferrocene, a series of vinyl-substituted phosphaferrocenes was prepared by Wittig and related olefination reactions. The parent 3,4dimethyl-2-vinylphosphaferrocene (2) could be selectively converted to either the terminal or branched alcohols 8b and 8a by hydroboration/oxidation or protonation in aqueous solution, respectively. Elimination of HBr from 2-bromovinylphosphaferrocene 9 provided access to the 2-ethynylphosphaferrocene derivative 10, which could be converted to other alkynes by deprotonation and electrophilic quench. Additionally, the syntheses of the 2-cyano-(15) and 2-Synthesis and Reactivity of Vinyl-and Alkynylphosphaferrocenes Scheme 1. Preparation of the vinylphosphaferrocene derivative 2.are easily accessible by Horner-Wadsworth-Emmons reactions (Scheme 2). [7] The desired phosphonates were obtained from triethyl phosphite and the respective bromo compound and were subsequently deprotonated with nBuLi or NaH prior to addition of the aldehyde. The acrylic ester 3 was obtained solely as the E isomer, whereas for the acrylonitrile 4 an E/Z ratio of 10:1 was observed. Scheme 2. Preparation of acrylic derivatives 3 and 4.The presence of the phosphorus atom affects the appearance of the 1 H NMR spectrum of the vinyl group in compound 2; the signal for the CH proton is additionally split due to a 3 J HP coupling of 10.5 Hz, whereas the trans proton of the CH 2 group experiences a 4 J HP coupling of 1.8 Hz.No H-P coupling was observed for the cis CH 2 proton. The acrylic ester 3 could be reduced to give the saturated compound 5 by treatment with NaBH 4 in the presence of CuCl [8] and was finally hydrolyzed to the propionic acid 6 (Scheme 3).Scheme 3. Preparation of propionic acid derivatives 5 and 6.Commencing from 2, the isomeric 2-(phosphaferrocenyl)ethanols 8a and 8b could be prepared. Thus, hydroboration of 2 yields the anti-Markownikow organoborane 7 as a mixture of diastereomers due to the racemic nature of compound 2. However, treatment with alkaline hydrogen peroxide cleanly afforded the linear alcohol 8b in 69 % overall yield, an alternative synthesis of which has been reported by our group before. [9] On the contrary, the branched isomer 8a was obtained by treatment of the vinyl derivative 2 with aqueous hydrochloric acid (Scheme 4). Presumably, the Eur.

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Section: Resultssupporting

confidence: 55%

Section: Carbonylcobalt Complexesmentioning

confidence: 65%

Section: Carbonylcobalt Complexesmentioning

confidence: 99%

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Unsaturated Organic Derivatives of Phosphaferrocene – Synthesis and Reactivity of Vinyl‐ and Alkynylphosphaferrocenes

2012

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“…The solvent was evaporated, saturated sodium bicarbonate solution was added, and the mixture was extracted with diethyl ether. Column chromatography (silica gel 60) of the crude product using 13 The same product 3 was obtained by treatment of 2 with TFA (10 mg/ml). The reaction was monitored by HPLC analysis of aliquots (10 ll) sampled from the mixture (containing 10 mg/ml formylferrocene as internal standard) in suitable time intervals.…”

Section: Rac-2 3-ferroceno-7-ferrocenyltropone (3)mentioning

confidence: 99%

Cyclisation of diferrocenylbutadiyne dicobalt hexacarbonyl mono-adduct to novel ferrocenotropones

Laus¹,

Schottenberger

Lukasser

et al. 2005

Journal of Organometallic Chemistry

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“…50 auf und kommen als Modellsysteme für molekulare Drähte infrage. [302] In den letzten Jahren wurde über eine Reihe von MetallFerrocenylalkinylkomplexen unter anderem mit Pt II , [295,303,304] Mn I , [305] Ru und Os, [131,[306][307][308][309][310] [Co 2 (CO) 6 ] [276,311,312] und Titanocen berichtet, [313] aus denen durch chemische oder elektrochemische Oxidation zweikernige gemischtvalente Heterometallkomplexe erhältlich sind. [314] Die Systeme lassen sich nach Robin und Day als gemischtvalente Verbindungen der Klasse II einstufen.…”

Section: Ferrocenylalkineunclassified

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

Long

Williams

2003

Angewandte Chemie

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Metallalkinylkomplexe bergen eine große Anziehungskraft für die Synthesechemie, die Strukturchemie und die Materialwissenschaften, sodass mittlerweile eine Vielzahl von Reaktionen zur M‐CC‐Verknüpfung mit einer ganzen Skala von Übergangsmetall‐ und Alkinylreagentien entwickelt wurde. Einige Methoden sind breit anwendbar, andere beschränken sich auf ein spezielles Metall oder Substrat. Wegen der linearen Geometrie der Alkinyleinheit und ihrem ungesättigten Charakter sind die Metallalkinyle attraktive Bausteine für molekulare Drähte und polymere metallorganische Materialien, die interessante physikalische Eigenschaften wie flüssigkristallines Verhalten, optische Nichtlinearität, Lumineszenz und elektrische Leitfähigkeit aufweisen können. Dieses einzigartige Spektrum an Eigenschaften steht als treibende Kraft hinter der intensiven Erforschung von Metall‐Alkinyl‐σ‐Komplexen. Die Entwicklung und Fortschritte insbesondere der letzten zehn Jahre werden in diesem Aufsatz zusammengefasst.

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Ferrocenylalkynes as ligands in transition metal complexes

Cited by 28 publications

References 30 publications

Unsaturated Organic Derivatives of Phosphaferrocene – Synthesis and Reactivity of Vinyl‐ and Alkynylphosphaferrocenes

Unsaturated Organic Derivatives of Phosphaferrocene – Synthesis and Reactivity of Vinyl‐ and Alkynylphosphaferrocenes

Cyclisation of diferrocenylbutadiyne dicobalt hexacarbonyl mono-adduct to novel ferrocenotropones

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

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