Reductive cleavage of resin bound arylsulfonates
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Cleavage (geology)
Carboxylate
Bond cleavage
Synthesis of carboxylate-bridged iron–thiolate clusters from alcohols/aldehydes or carboxylate salts
Carboxylate-bridged iron–thiolate clusters were formed from alcohols/aldehydes in air or sodium carboxylates at room temperature.
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Abstract Due to resurgence of applications of carboxylate complexes, there is a necessity to revisit the structural and synthetic aspects along with supramolecular aspects of carboxylate complexes of lower nuclearity and this article elaborates such aspects with a few selected examples limiting mononuclear to tetranuclear carboxylate complexes. ACKNOWLEDGEMENTS The author thanks the Department of Science and Technology, New Delhi, India, for financial support.
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Limiting
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The carboxylate stretching frequencies of two high-valent, di-μ-oxido bridged, manganese dimers has been studied with IR spectroscopy in three different oxidation states. Both complexes contain one monodentate carboxylate donor to each Mn ion, in one complex, the carboxylate is coordinated perpendicular to the Mn-(μ-O)2-Mn plane, and in the other complex, the carboxylate is coordinated in the Mn-(μ-O)2-Mn plane. For both complexes, the difference between the asymmetric and the symmetric carboxylate stretching frequencies decrease for both the Mn2IV,IV to Mn2III,IV transition and the Mn2III,IV to Mn2III,III transition, with only minor differences observed between the two arrangements of the carboxylate ligand versus the Mn-(μ-O)2-Mn plane. The IR spectra also show that both carboxylate ligands are affected for each one electron reduction, i.e., the stretching frequency of the carboxylate coordinated to the Mn ion that is not reduced also shifts. These results are discussed in relation to FTIR studies of changes in carboxylate stretching frequencies in a one electron oxidation step of the water oxidation complex in Photosystem II.
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Oxygen-evolving complex
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Cleavage (geology)
Cyanogen bromide
Bond cleavage
Peptide bond
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In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxyl-ate group. The cyclo-butane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and 0.118 (7). In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3 (+)) and donor (through a single carboxylate O from two different aminocyclobutane carb-oxylate moities)], resulting in a two-dimensional layered structure lying parallel to (100).
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Acceptor
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A novel pyrazolate-based diiron(II) complex shows five different binding modes of exogenous carboxylate ligands in a single crystal structure. Temperature dependent X-ray data reveal thermally induced disorder due to carboxylate dynamics that resemble the carboxylate shift, as it is known from various diiron enzyme active sites.
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Enhancing reactivity: A common feature of non-heme iron enzymes is the presence of carboxylate groups. An axial carboxylate group has been introduced trans to the oxo group of a non-heme oxoiron(IV) complex (see scheme). The coordination of carboxylate destabilizes the FeIVO unit and activates it towards reaction with dihydroanthracene.
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Reactivity
Coordination complex
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In this chapter, strategies for lignin linkages cleavage beginning with C α O–H/ArO–H or C α –OH bonds heterolysis are summarized, primarily focusing on lignin alkaline hydrolysis, acidolysis, and their corresponding tandem processes. Chapter 8.1 focuses on the base-catalyzed cleavage of the C β –OAr bond beginning with C α O–H or ArO–H heterolysis to oxygen anion, which further induces the cleavage of the lignin C β –OAr bond. Chapter 8.2 summarizes the various acid-catalyzed methods for the C β –OAr bond cleavage beginning with C α –OH heterolysis, which further induce the C β –OAr bond cleavage via a C α =C β –OAr intermediate.
Heterolysis
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Bond cleavage
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