On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

Jäger, Lothar; Tretner, C.; Hartung, H.; Biedermann, M.

doi:10.1002/(sici)1099-0682(199807)1998:7<1051::aid-ejic1051>3.0.co;2-c

Cited by 14 publications

(2 citation statements)

References 22 publications

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“…[16][17][18] Pioneering theoretical work by Clark uncovered the importance of odd-electron interactions with metal ions in the radical addition reactions of nonpolar alkenes 19,20 and several radical ring closures (the so-called "radical-clock" reactions). 21,22 More than 25 years ago, Clark predicted that radical addition to nonpolar alkenes could be catalyzed by coordination of Li + to the C C bond. 19 Michl et al later experimentally verified this prediction, finding that the Li + salts of a noncoordinating carboborane anion could facilitate the radical polymerization of 1-alkenes by catalyzing propagation over the degenerative hydrogen transfer reactions that otherwise impede the formation of polymer.…”

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Isotactic Regulation in the Radical Polymerization of Calcium Methacrylate: Is Multiple Chelation the Key to Stereocontrol?

Noble

Coote

2019

Journal of Polymer Science

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Accurate quantum chemistry is used to explain the origins of isospecificity in radical polymerization of calcium methacrylate hydrate (CaMA). Distonic radical–cation interactions are shown to be crucial in determining the reactivity of different coordination structures. Cation coordination to the terminal and incoming monomer side chains reduces radical‐cation separation, enhancing the reactivity of these modes over the stereocontrolling terminal‐penultimate binding modes. This explains why Lewis acid‐mediated radical polymerization often fails to produce highly isotactic polymer for common monomers such as methyl methacrylate. However, theoretical calculations suggest that the poly(CaMA) terminus forms a chelated bridging scaffold in N,N‐dimethylformamide (DMF), which involves the terminal, penultimate and incoming monomer carboxylate groups. This scaffold simultaneously activates the incoming monomer toward propagation and regulates the relative orientation of the terminal and penultimate side chains. The bridging scaffold is disrupted in more polar solvents and/or if alternative nonchelating counter‐cations are employed, leading to loss of isotactic control. These results suggest that higher levels of isotactic control may be achievable if reaction conditions are optimized to favor bridging scaffold formation. The broader importance of these findings to stereocontrol in radical polymerization is also discussed. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 52–61

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confidence: 99%

Isotactic Regulation in the Radical Polymerization of Calcium Methacrylate: Is Multiple Chelation the Key to Stereocontrol?

Noble

Coote

2019

Journal of Polymer Science

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“…One of the currently three known FRs (FR-α, FR-β, and FR-γ), it is abundantly expressed on activated macrophages, particularly of the M2 subset, which are specifically common in RA synovium [83] and in atherosclerotic plaques. [84] Importantly, in RA, FR-β is specifically expressed by macrophages, but not by T cells in synovium, nor by circulating T cells or monocytes. [85] • CD44 is a cell surface glycoprotein encoded by a single gene with multiple splice variants; therefore, various isoforms exist for CD44, [86] and they are associated to, e.g.…”

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Fishing for fire: strategies for biological targeting and criteria for material design in anti‐inflammatory therapies

d’Arcy

Tirelli

2014

Polymers for Advanced Techs

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Inflammatory pathologies are a growing burden for developed societies, and the tools offered by medicinal chemistry/biotechnology have provided us with an armamentarium of active principles. Unfortunately, most of them are marred by very significant side effects that can be summarized by two words: poor targeting (of cells, of tissues, etc.). This review provides a broad overview of the approaches and of the materials used to obtain an inflammation‐responsive or inflammation‐targeted behavior, which can be used to improve anti‐inflammatory therapies. Here, we first define the biochemical factors that may allow both to recognize and to target an inflamed environment, for example, the leakiness of capillaries, the presence of oxidants (reactive oxygen species), or of upregulated receptors/enzymes. We then review the systems that have shown the possibility to accumulate in inflamed tissues, respond to its stimuli, or bind to activated inflammatory cells, separately discussing payload/carrier (guest/host) systems and macromolecular prodrugs/conjugates. Copyright © 2014 John Wiley & Sons, Ltd.

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Electrochemical Synthesis of Tricyanomethyl Copper Complexes

Kamte¹,

Baumeister²,

Schäfer³

2003

Zeitschrift anorg allge chemie

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The synthesis of tricyanomethyl copper complexes has been achieved by anodic dissolution of a sacrificial copper metal and cathodic reduction of 1,1,3,3-tetracyanopropane in acetonitrile, in the presence of triphenylphosphane used as coligand. The electrogenerated tetracyanopropyl radical anion is not stable and undergoes a cleavage leading to the tricyanomethyl anion and acrylonitrile which is electropolymerized at the cathode. The reaction solution gives a neutral dimeric binuclear copper(I) complex, bis{(µtricyanomethanido)bis(triphenylphosphane)copper(I)}[Cu(µ-

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On the Ambident Behaviour of Dicyanmethanidonitrite; Syntheses and Characterization of Complexes of the Type [M{N(O)C(CN)2}(PPh3)n] (M = CuI, AgI;n = 2, 3)

Cited by 14 publications

References 22 publications

Isotactic Regulation in the Radical Polymerization of Calcium Methacrylate: Is Multiple Chelation the Key to Stereocontrol?

Isotactic Regulation in the Radical Polymerization of Calcium Methacrylate: Is Multiple Chelation the Key to Stereocontrol?

Fishing for fire: strategies for biological targeting and criteria for material design in anti‐inflammatory therapies

Electrochemical Synthesis of Tricyanomethyl Copper Complexes

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