Ethynylcobaltocenium compounds as precursors for bridged, heteronuclear oligometallocenes

Wildschek, Michael; Rieker, Christopher; Jaitner, Peter; Schottenberger, Herwig; Schwarzhans, Karl E.

doi:10.1016/0022-328x(90)85476-f

Cited by 36 publications

(33 citation statements)

References 20 publications

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“…Dichloromethane was distilled from calcium hydride just before use. 1 Click Synthesis of 7: The compound 7 was synthesized according to the same procedure as for 1 above by the click synthesis between (azidomethyl)ferrocene [53] (80 mg, 0.33 mmol) and ethynylcobalticinium hexafluorophosphate [52] (118.84 mg, 0.33 mmol) and obtained as orange-red needles after precipitation in ether; yield 84 %. Ethynylferrocene, styrene, benzyl azide, and Me 3 OBF 4 were purchased from Aldrich.…”

Section: Methodsmentioning

confidence: 99%

Click Synthesis and Redox Chemistry of Mono‐ and Heterobimetallic Triazolyl and Triazolium‐Ferrocene and Cobalticinium Complexes

et al. 2012

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Mono-and heterobimetallic triazolylferrocene and cobalticinium complexes and triazolium derivatives were synthesized by click reactions between the ethynylmetallocenes and benzyl azide or (azidomethyl)ferrocene followed by methylation reactions, respectively. Cyclic voltammetry data shed light on the electron-withdrawing character of the 1,2,3-triazolyl and triazolium substituents of the metallo-[a] ISM,

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Section: Methodsmentioning

confidence: 99%

Click Synthesis and Redox Chemistry of Mono‐ and Heterobimetallic Triazolyl and Triazolium‐Ferrocene and Cobalticinium Complexes

et al. 2012

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“…[14] The reaction between 1 and the commercially available first-generation poly(amido amine) (PAMAM) dendri-mer that contained eight terminal NH 2 groups (20 wt % solution in MeOH) in CH 3 CN/CH 2 Cl 2 (1:1) at 35 8C for two days yields the all-trans-enamine-cobalticenium dendrimer 2 (Scheme 1). The color of the mixture changed from yellow to deep red while stirring the reaction mixture, which indicates the formation of the enamine product.…”

Section: Resultsmentioning

confidence: 99%

“…This latter reaction of readily available ethynylcobalticenium hexafluorophosphate [14,15] with primary and secondary amines is facile, quantitative, and does not form byproducts. It yields air-stable, strongly colored push-pull conjugated cobalticenium trans-enamines and thus appears to be an ideal "green" reaction for the efficient and facile functionalization of a variety of aminated dendrimers.…”

Section: Introductionmentioning

confidence: 95%

Metalation of Polyamine Dendrimers with Ethynylcobalticenium for the Construction of Mono‐ and Heterobimetallic Polycationic Metallodendrimers

Wang

Rapakousiou

Ruiz

et al. 2014

Chemistry A European J

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The introduction of robust redox groups at the periphery of common amine-terminated dendrimers is of interest in the design of dendritic nanobatteries, sensors, and redox catalysts. Here we are applying the recently discovered uncatalyzed hydroamination of ethynylcobalticenium, a mild "green" reaction that quantitatively yields trans-enamines without the formation of any byproduct, to functionalize dendrimers that are terminated with primary or secondary amino groups. Poly(amido amine) (PAMAM) dendrimers terminated by primary amino groups and arene-centered dendrimers terminated by secondary amino groups yield dendrimers that contain up to 81 trans-enamine-cobalticenium termini using this reaction. The hydroamination reaction was also conducted with dendrimers that contained ferrocenylmethylamino groups, which yielded dendrimers that contained both ferrocenyl and cobalticenium termini. The size of the dendrimers was investigated using both dynamic light scattering and diffusion-ordered spectroscopy (DOSY) 1 H NMR spectroscopy, and the number of electrons involved in heterogeneous multielectron transfers at electrodes was searched by cyclic voltammetry. The latter works well up to the 27-branch dendrimer, whereas the 81-dendrimer yielded a result in an excess amount (110 electrons) owing to adsorption onto the cathode that becomes all the more significant as the metallodendrimer size increases.

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“…ferrocene), it is very challenging to carry out direct electrophilic substitution on the charged cobaltocenium, which is a key hurdle in cobaltocenium chemistry (9). Basically, two approaches have been established to synthesize mono-substituted cobaltocenium, as shown in Scheme 1: (i) a statistical reaction between methyl cyclopentadiene, cyclopentadiene and cobalt bromide, followed by further oxidation and exhausted separation to give cobaltocenium monoacid, which can be further converted into vinyl monomers (method 1 in Scheme 1) (9); (ii) reaction between un-substituted cobaltocenium and a nucleophile based on organolithium reagents, followed by hydride abstraction to give mono-substituted cobaltocenium (method 2 in Scheme 1) (21)(22)(23). Due to the nature of the statistical reaction, the first method (method 1) is very tedious and produces low yield (ca.…”

Section: Synthesis Of Mono-substituted Cobaltocenium Derivatives and mentioning

confidence: 99%

Side-Chain Cobaltocenium-Containing Polymers: Controlled Polymerization and Applications

Yan

Zhang

Tang

2015

ACS Symposium Series

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Due to the cationic nature, cobaltocenium-containing polymers are novel metal-containing polyelectrolytes, which could find applications in the fields of magnetic materials, stimuliresponsive materials, chemical/bio sensors and antimicrobials. More interestingly, these polymers show counterion-dependent solubility and hereinafter unique properties.Functional cobaltocenium-containing polymers can be prepared through either direct polymerization of cobaltocenium-functionalized monomers or post-polymerization modification of precursor polymers.This chapter summarizes the most recent progress of side-chain cobaltocenium-containing polymers via controlled polymerization methods, such as ATRP, RAFT, and ROMP. Different methods involving the synthesis of cobaltocenium-containing monomers are discussed. Furthermore, self-assembly and biomedical applications of these metallopolymers in the field of antimicrobials are introduced.

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Ethynylcobaltocenium compounds as precursors for bridged, heteronuclear oligometallocenes

Cited by 36 publications

References 20 publications

Click Synthesis and Redox Chemistry of Mono‐ and Heterobimetallic Triazolyl and Triazolium‐Ferrocene and Cobalticinium Complexes

Click Synthesis and Redox Chemistry of Mono‐ and Heterobimetallic Triazolyl and Triazolium‐Ferrocene and Cobalticinium Complexes

Metalation of Polyamine Dendrimers with Ethynylcobalticenium for the Construction of Mono‐ and Heterobimetallic Polycationic Metallodendrimers

Side-Chain Cobaltocenium-Containing Polymers: Controlled Polymerization and Applications

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