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Evidence for a Precursor Complex in CH Hydrogen Atom Transfer Reactions Mediated by a Manganese (IV) Oxo Complex

Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2011, vol.123, núm. 25, p. 5766-5771. DOI http://dx.doi.org/10.1002/ange.201100907

HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies

We thank Prof. Jim Mayer and Dr. Julio Lloret for reading this work and for helpful comments. M. C. thanks MICINN (CTQ2009-08464/BQU and PhD grants to I.G.-B) and the European Research Council (ERC-StG-239910). M. C. and X. R. acknowledge ICREA-Academia Awards, and SGR 2009-SGR637. S. S. thanks the Swedish Energy Agency, The K&A Wallenberg Foundation, and the EU/Energy project "SOLAR-H2". W. R. B. thanks Netherlands Technology Foundation STW grant no. 11059

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Garcia Bosch, Isaac
Company Casadevall, Anna
Cady, Clyde W.
Styring, Stenbjörn
Browne, Wesley R.
Ribas Salamaña, Xavi
Costas Salgueiro, Miquel
Abstract: Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2011, vol.123, núm. 25, p. 5766-5771. DOI http://dx.doi.org/10.1002/ange.201100907
HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies
We thank Prof. Jim Mayer and Dr. Julio Lloret for reading this work and for helpful comments. M. C. thanks MICINN (CTQ2009-08464/BQU and PhD grants to I.G.-B) and the European Research Council (ERC-StG-239910). M. C. and X. R. acknowledge ICREA-Academia Awards, and SGR 2009-SGR637. S. S. thanks the Swedish Energy Agency, The K&A Wallenberg Foundation, and the EU/Energy project "SOLAR-H2". W. R. B. thanks Netherlands Technology Foundation STW grant no. 11059
Document access: http://hdl.handle.net/2072/300369
Language: eng
Rights: Tots els drets reservats
Subject: Metalls de transició -- Compostos
Transition metal compounds
Manganès -- Compostos
Manganese compounds
Cinètica química
Chemical kinetics
Title: Evidence for a Precursor Complex in CH Hydrogen Atom Transfer Reactions Mediated by a Manganese (IV) Oxo Complex
Type: info:eu-repo/semantics/article
Repository: Recercat

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