Diagnosis of Magnetoresponsive Aromatic and Antiaromatic Zones in Three-Membered Rings of d- and f-Block Elements
Φόρτωση...
Ημερομηνία
Συγγραφείς
Tsipis, A. C.
Depastas, I. G.
Karagiannis, E. E.
Tsipis, C. A.
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Εκδότης
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Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
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Όνομα περιοδικού
Journal of Computational Chemistry
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Περιγραφή
Magnetoresponsive three-membered rings of d- and f-block elements have been thoroughly investigated with file help of electronic structure calculation methods. The magnetic response of the clusters was evaluated by the Nucleus Independent Chemical Shifts (NICS)(zz)-scan curves, which in conjunction with symmetry-based selection rules for the most significant translationally and rotationally allowed transitions helped rationalize and predict the orbital-type of aromaticity/antiaromaticity of the clusters. The magnetoresponsive early (Groups 3, 4, and 5) transition metal M(3) rings exhibit successive aromatic and antiaromatic zones separated by a nodal plane. The magnetoresponsive late (Groups 11 and 12) transition metal M(3) rings exhibit long-range aromatic zone with the NICS(zz)(R) values decaying rapidly and monotonically with respect to R. The magnetic response of Group 10 transition metal M(3) rings is similar to that of the early transition metal M(3) rings, but it is long-range antiaromatic only for the [c-Ni(3)] cluster. The NICS(zz)-scan curve of the [(H(t)La)(3)(mu(2)-H)(6)] cluster is indicative of weak pure sigma-aromaticity due to the induced diatropic ring current from the translationally allowed a(1)' -> e' and e' -> a(1)' transitions. The aromatic-antiaromatic behavior of the [(H(t)Ce)(3)(mu(2)-H)(6)](+) and [(H(t)Tm)(3)(mu(2)-H)(6)](2-) clusters is similar to that of the early d-block elements. The magnetic response of [(H(t)Yb)(3)(mu(2)-H)(6)](3-) is similar to that of [c-Hg(3)](2-). The [(H(t)Lu)(3)(mu(2)-H)(6)] cluster can be considered as a doubly (sigma + pi) aromatic system, with the sigma-aromatic component being much stronger than the pi-aromatic one. Finally, the [(X(t)Re)(3)(mu(2)-X)(6)] and [(X(t)Ru)(3)(mu(2)-X)(6)](+) (X = Cl, Br, I) clusters exhibit significant aromatic character with the greatest contribution to the induced diatropic ring currents coming from pi-type transitions. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 31: 431-446, 2010
Περιγραφή
Λέξεις-κλειδιά
aromaticity, dft calculations, nics(zz)-scan profiles, aromatic zones, antiaromatic zones, aromaticity of d- and f-block clusters, independent chemical-shifts, zeta-valence quality, gaussian-basis sets, current-density, continuous transformation, electron delocalization, orbital contributions, magnetic-properties, nics profiles, atoms li
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<Go to ISI>://000273412900018
http://onlinelibrary.wiley.com/store/10.1002/jcc.21327/asset/21327_ftp.pdf?v=1&t=h0f911xv&s=7f82a949e6ebd560fe88a88bdf26e0d0428b1505
http://onlinelibrary.wiley.com/store/10.1002/jcc.21327/asset/21327_ftp.pdf?v=1&t=h0f911xv&s=7f82a949e6ebd560fe88a88bdf26e0d0428b1505
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en
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Γενική Περιγραφή / Σχόλια
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Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας