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Analysis of the aromaticity of five-membered heterometallacycles containing Os, Ru, Rh, and Ir

We study the molecular structure and aromaticity in a series of experimental and new in silico designed five-membered heterometallacycles with general formula M(XC3H3)(PH3)2, where M = OsH3, OsCl3, OsCl2, RuCl2, RhCl2 or IrCl2 and X = NH, O, S, CH-, or CH+. The electron delocalization of the five-membered rings in these complexes is analyzed using the induced magnetic field, NICS, and MCI descriptors of aromaticity. Our results indicate that the five-membered rings in all complexes with X = NH, O, S, and CH- have a low aromatic character denoted by nonintense diatropic behavior and low MCI values. Five-membered rings in complexes with X = CH+ are clearly paratropic and antiaromatic according to MCI values with the exception of M = OsCl 3. The reason for this exception is discussed

The authors are grateful to the Research Executive Agency of the European Research Council for financial support through the PIRSES-GA-2009-247671 project of the FP7-PEOPLE-2009-IRSES program. R.I. thanks the same organization for the postdoctoral fellowship received from the same project. M.S. and J.P. are grateful to the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086), the Generalitat de Catalunya (project numbers 2009SGR637 and 2009SGR528, Xarxa de Referencia en Quimica Teorica i Computacional, and ICREA Academia 2009 prize for M.S.), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. The Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is acknowledged for a generous allocation of computer time

© Organometallics, 2014, vol. 33, p. 1762-1773

American Chemical Society (ACS)

Autor: Islas, Rafael
Poater i Teixidor, Jordi
Solà i Puig, Miquel
Data: 2014
Resum: We study the molecular structure and aromaticity in a series of experimental and new in silico designed five-membered heterometallacycles with general formula M(XC3H3)(PH3)2, where M = OsH3, OsCl3, OsCl2, RuCl2, RhCl2 or IrCl2 and X = NH, O, S, CH-, or CH+. The electron delocalization of the five-membered rings in these complexes is analyzed using the induced magnetic field, NICS, and MCI descriptors of aromaticity. Our results indicate that the five-membered rings in all complexes with X = NH, O, S, and CH- have a low aromatic character denoted by nonintense diatropic behavior and low MCI values. Five-membered rings in complexes with X = CH+ are clearly paratropic and antiaromatic according to MCI values with the exception of M = OsCl 3. The reason for this exception is discussed
The authors are grateful to the Research Executive Agency of the European Research Council for financial support through the PIRSES-GA-2009-247671 project of the FP7-PEOPLE-2009-IRSES program. R.I. thanks the same organization for the postdoctoral fellowship received from the same project. M.S. and J.P. are grateful to the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086), the Generalitat de Catalunya (project numbers 2009SGR637 and 2009SGR528, Xarxa de Referencia en Quimica Teorica i Computacional, and ICREA Academia 2009 prize for M.S.), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. The Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is acknowledged for a generous allocation of computer time
Format: application/pdf
ISSN: 0276-7333 (versió paper)
1520-6041 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/10191
Llenguatge: eng
Editor: American Chemical Society (ACS)
Col·lecció: MICINN/PN 2012-2014/CTQ2011-23156
MICINN/PN 2012-2014/CTQ2011-25086
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-528
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/om500119c
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/247671
És part de: © Organometallics, 2014, vol. 33, p. 1762-1773
Drets: Tots els drets reservats
Matèria: Compostos organometàl·lics
Organometallic compounds
Aromaticitat (Química)
Aromaticity (Chemistry)
Títol: Analysis of the aromaticity of five-membered heterometallacycles containing Os, Ru, Rh, and Ir
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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