Strained Ferrocenophanes

Musgrave, Rebecca A.; Russell, Andrew D.; Manners, Ian

doi:10.1021/om400488k

Cited by 82 publications

(87 citation statements)

References 129 publications

(354 reference statements)

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“…1b) where the inherent ring strain acts as a thermodynamic driving force for the ROP process. 20,21 This strain can be quantified by the angle between the Cp ring planes (α) and several other structural parameters (Fig. 1b).…”

Section: Introductionmentioning

confidence: 99%

Main-chain metallopolymers at the static–dynamic boundary based on nickelocene

et al. 2017

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. AbstractInteractions between metal ions and ligands in metal-containing polymers involve two bonding extremes: persistent covalent bonding, where the polymers are essentially static in nature, or labile coordination bonding, which leads to dynamic supramolecular materials.Main chain polymetallocenes based on ferrocene and cobaltocene fall into the former category due to the presence of strong metal-cyclopentadienyl bonds. Herein we describe a main chain polynickelocene formed by ring-opening polymerization of a moderately strained[3]nickelocenophane monomer, that can be switched between static and dynamic states as a result of the relatively weak Ni-cyclopentadienyl ligand interactions. This is illustrated by the observation that, at low concentration or at elevated temperature in a coordinating or polar solvent, depolymerization of the polynickelocene occurs. A study of this dynamic polymermonomer equilibrium by 1 H NMR spectroscopy allowed for determination of the associated thermodynamic parameters. Microrheology data, however, indicated that under similar conditions the polynickelocene is considered to be static on the shorter, rheological timescale.2

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Section: Introductionmentioning

confidence: 99%

Main-chain metallopolymers at the static–dynamic boundary based on nickelocene

et al. 2017

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“…[2] Significant advances in the synthesis and purification of monomers and in polymerization methods were made during the last two decades, in particular for the class of ferrocenophanes (FCPs). [3] The most developed strained sandwich compounds are silicon-bridged [1]FCPs (A; Figure 1), which can undergo living polymerization, [2,4] allowing the preparation of block copolymers. Poly(ferrocenyldimethylsilane) (PFS with SiMe 2 ; Figure 1) is partially crystalline, causing block copolymers to form rod-shaped micelles in block-selective solvents with PFS as the core.…”

Section: Introductionmentioning

confidence: 99%

Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

Sadeh

Bhattacharjee

Sarbisheh

et al. 2014

Chemistry A European J

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A series of new boron-bridged [1]ferrocenophanes ([1]FCPs) was prepared by salt-metathesis reactions between enantiomerically pure dilithioferrocenes and amino(dichloro)boranes (Et2 NBCl2 , iPr2 NBCl2 , or tBu(Me3 Si)NBCl2 ). The dilithioferrocenes were prepared in situ by lithium-bromine exchange from the respective planar-chiral dibromides (Sp ,Sp )-[1-Br-2-(HR2 C)H3 C5 ]2 Fe (R=Me or Et). In most of the cases, mixtures of the targeted [1]FCPs 4 and the unwanted 1,1'-bis(boryl)ferrocenes 5 were formed. The product ratio depends on the bulkiness of the amino group, the speed of addition of the amino(dichloro)borane, the alkyl group on Cp rings, and in particular on the reaction temperature. The formation of strained [1]FCPs is strongly favored by increased reaction temperatures. Secondly, CHEt2 groups at Cp rings favored the formation of the targeted [1]FCPs stronger than CHMe2 groups. These discoveries open up new possibilities to further suppress the formation of unwanted byproducts by a careful choice of the reaction temperature and through tailoring the bulkiness of CHR2 groups on ferrocene. Thermal ring-opening polymerizations of selected boron-bridged [1]FCPs gave metallopolymers with a Mw of 10 kDa (GPC).

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“…[1e],[29]À [30] Especially, ferrocenyl moiety attached to azaheterocycles through N-alkylamino linkage displayed interesting medicinal properties, for example, ferroquine, an analogues of chloroquine with aminoquinoline and ferrocene moieties is an antimalarial drug. [31] Owing to the importance of .…”

Section: Resultsmentioning

confidence: 99%

Cu-Catalyzed Expeditious Synthesis of N-Benzylaminoheter-ocycles Using N-Tosylhydrazones and Aminoheteroarenes

et al. 2016

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N‐Tosylhydrazones were successfully coupled in the presence of CuI (10 mol%) with various heterocyclic amines to develop a convenient and high yielding protocol for the preparation of N‐benzylaminoheterocycles under microwave irradiation. This ligand‐free new methodology uses readily available starting materials and a cheaper copper catalyst. A wide range of O, N and S containing heteroarylamines and o‐phenylenediamine were explored to prepare N‐benzylaminoheterocycles and 1,2‐disubstituted benzimidazoles. The protocol was equally effective with N‐tosylhydrazones derived from aldehydes and ketones, especially ferrocene aldehyde to prepare an array of N‐benzylaminoheterocycles in good to excellent yields. Finally, the identified reaction conditions were utilized to prepare drug‐like molecules namely pyrido[1,2‐a]benzimidazole and N‐substituted‐2‐amino‐thiazole derivative as antitubercular agents.

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Strained Ferrocenophanes

Cited by 82 publications

References 129 publications

Main-chain metallopolymers at the static–dynamic boundary based on nickelocene

Main-chain metallopolymers at the static–dynamic boundary based on nickelocene

Chiral Bora[1]ferrocenophanes: Syntheses, Mechanistic Insights, and Ring‐Opening Polymerizations

Cu-Catalyzed Expeditious Synthesis of N-Benzylaminoheter-ocycles Using N-Tosylhydrazones and Aminoheteroarenes

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