The Origins of Dramatic Axial Ligand Effects: Closed‐Shell Mn V O Complexes Use Exchange‐Enhanced Open‐Shell States to Mediate Efficient H Abstraction Reactions
2012; Wiley; Volume: 124; Issue: 18 Linguagem: Inglês
10.1002/ange.201200689
ISSN1521-3757
AutoresDeepa Janardanan, Dandamudi Usharani, Sason Shaik,
Tópico(s)Magnetism in coordination complexes
ResumoAngewandte ChemieVolume 124, Issue 18 p. 4497-4501 Zuschrift The Origins of Dramatic Axial Ligand Effects: Closed-Shell MnVO Complexes Use Exchange-Enhanced Open-Shell States to Mediate Efficient H Abstraction Reactions† Dr. Deepa Janardanan, Dr. Deepa Janardanan Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this authorDr. Dandamudi Usharani, Dr. Dandamudi Usharani Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this authorProf. Dr. Sason Shaik, Corresponding Author Prof. Dr. Sason Shaik [email protected] Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this author Dr. Deepa Janardanan, Dr. Deepa Janardanan Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this authorDr. Dandamudi Usharani, Dr. Dandamudi Usharani Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this authorProf. Dr. Sason Shaik, Corresponding Author Prof. Dr. Sason Shaik [email protected] Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)Search for more papers by this author First published: 21 March 2012 https://doi.org/10.1002/ange.201200689Citations: 6 † Support by Minerva is thanked. Prof. H. Schwarz is thanked for pointing out the closed–open issue and reading the paper. Read the full textAboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Spinzustandseffekte: Trotz geschlossenschaliger Singulett-Grundzustände ist in [(Cz)MnVO]-Komplexen der reaktive Zustand ein offenschaliges B-Triplett (SB=1), das hohen Oxyl-Radikalcharakter hat und einen durch austauschverstärkte Reaktivität (EER) stabilisierten Übergangszustand (TS) aufweist (siehe Bild). Der drastische axiale Ligandeneffekt hat seine Ursache in der EER dieses Zustands. Supporting Information Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description ange_201200689_sm_miscellaneous_information.pdf3.9 MB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aThe ground state of MnIV complexes is generally S=3/2. See discussion in: R. S. Czernuszewicz, Y. O. Su, M. K. Stern, K. A. Macor, D. Kim, J. T. Groves, T. G. Spiro, J. Am. Chem. Soc. 1988, 110, 4158–4165; 10.1021/ja00221a010 CASWeb of Science®Google Scholar 1bM. F. Ryan, A. Fiedler, D. Schröder, H. Schwarz, J. Am. Chem. 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