Polymerization of monosubstituted acetylenes with a zwitterionic rhodium(I) complex, Rh+(2,5-norbornadiene)[.eta.6-C6H5)B-(C6H5)3]

Kishimoto, Y.; Itou, Masamichi; Miyatake, Tatsuya; Ikariya, Takao; Noyori, Ryoji

doi:10.1021/ma00123a037

Cited by 176 publications

(129 citation statements)

References 13 publications

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“…with an increase in the DP of macro-1 m , suggesting that the helical sense bias of macro-1 m can persist only in a rather short range from the α-end because of helix reversal. The macromonomers were then polymerized with a zwitterionic rhodium complex, 9 Rh…”

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confidence: 99%

Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant

et al. 2012

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Helical polymer brushes with a preferred-handed helix-sense composed of a poly(phenylacetylene) backbone and poly(phenyl isocyanate) pendants are synthesized. The helixsense of the backbone is effectively controlled by the helical chirality of the pendants, which is triggered by an optically 10 active group introduced at the pendant terminal. anticipated that the helix-sense bias of the polyacetylene backbone in the polymer brushes would be hierarchically induced by the helical chirality of the pendant polyisocyanate chains triggered by the terminal optically active group based on the covalent-bonding "chiral domino effect", 5,6 which further results 45 in a helical array of the helical polyisocyanate pendants with a preferred-handed helix-sense (Fig. 1). Table 1). 5b,7 The -NH terminated polymers that had not been end-capped with a 4-ethynylbenzoyl 65 group were completely removed by selective depolymerization in

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Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant

et al. 2012

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“…Materials: 4-Iodophenyl 3,4,6,-tri-O-acetyl-2-N-acetyl-b-d-glucopyranoside, [42] [43] methyl (4-iodophenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-dglycero-a-d-galacto-2-nonulopyranosid)onate, [44] and [45] were synthesized by previously reported methods. Trimethylsilylacetylene was kindly supplied by Shinetsu Chemical Co. and was used without further purification.…”

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Enhancement of Plant and Bacterial Lectin Binding Affinities by Three‐Dimensional Organized Cluster Glycosides Constructed on Helical Poly(phenylacetylene) Backbones

et al. 2010

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A series of poly(phenylacetylene)s bearing diverse saccharide pendants--N-acetyl-D-glucosamine, D-lactose, and N-acetyl-D-neuraminic acid--were synthesized by rhodium-mediated polymerizations of the corresponding acetyl-protected glycosylated phenylacetylenes followed by deprotection. The circular dichroism spectra of these glycosylated poly(phenylacetylene)s each displayed split-type Cotton effects in the long absorption region of the conjugated polymer backbone (260-500 nm), thus indicating predominantly one-handed helical conformations in their backbones. The binding affinities of these glycosylated poly(phenylacetylene)s, and those of previously reported phenylacetylenes bearing D-galactose, towards plant and bacterial lectins were investigated by hemagglutination inhibition assay and isothermal titration calorimetry (ITC). The stoichiometries of binding vary strongly, depending on the lectin binding sites and the accessibilities of the carbohydrate residues in the helices. The measured affinities also vary, with the maximum value observed for the interaction between poly-PA-α-Gal and lectin I from Pseudomonas aeruginosa, with a K(d) value of 4 μM per monosaccharide representing a 200-fold increase relative to the corresponding monomer.

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“…[45,[70][71][72][73][74][75] The performance of zwitterionic 3 was found to be divergent from, or superior to, that of more conventional neutral and cationic complexes in a number of catalytic applications. For example, whereas 95:5 branched selectivity was achieved in the reductive carbonylation of styrene using 3 (1 mol %) as a pre-catalyst, lower selectivity was achieved under similar conditions using either the cationic species [Rh(cod)(PPh 3 :20).…”

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Zwitterionic Relatives of Cationic Platinum Group Metal Complexes: Applications in Stoichiometric and Catalytic σ‐Bond Activation

2010

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Zwitterionic platinum group metal complexes that feature formal charge separation between a cationic metal fragment and a negatively charged ancillary ligand combine the desirable reactivity profile of related cationic complexes with the broad solubility and solvent tolerance of neutral species. As such, zwitterionic complexes of this type have emerged as attractive candidates for a diversity of applications, most notably involving the breaking and/or forming of E-H and E-C sigma bonds involving a main group element E. Important advances in ancillary ligand design are documented that have enabled the construction of platinum group metal zwitterions. Also summarized are the results of stoichiometric and catalytic investigations in which the reactivity of such zwitterions and their more traditionally employed cationic relatives in sigma bond activation chemistry are compared and contrasted.

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Polymerization of monosubstituted acetylenes with a zwitterionic rhodium(I) complex, Rh+(2,5-norbornadiene)[.eta.6-C6H5)B-(C6H5)3]

Cited by 176 publications

References 13 publications

Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant

Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant

Enhancement of Plant and Bacterial Lectin Binding Affinities by Three‐Dimensional Organized Cluster Glycosides Constructed on Helical Poly(phenylacetylene) Backbones

Zwitterionic Relatives of Cationic Platinum Group Metal Complexes: Applications in Stoichiometric and Catalytic σ‐Bond Activation

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