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Probing valence and spin situations in selective ruthenium–iminoquinonoidframeworks. An experimental and DFT analysis
2011 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 374, 216-225 p.Article in journal (Refereed) Published
Abstract [en]

The ruthenium–iminoquinone complexes, [Ru(tpm)(Cl)(Q)]+ [tpm = tris(1-pyrazolyl)methane, Q = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, where aryl = C6H5, [1]+; m-(OCH3)2C6H3, [2]+;m-(Cl)2C6H3, [3]+] have been synthesized. The sensitive bond distances of ‘‘Q’’ in [1](ClO4) and[2](ClO4), C–O: 1.294(8), 1.281(2) Å; C–N: 1.352(8), 1.335(2) Å; and C–C(meta): 1.366(10)/1.367(9) Å,1.364(2)/1.353(2) Å, respectively, and other analytical as well as theoretical (DFT) events suggest thevalence configuration of [RuIII(tpm)(Cl)(QSq)]+ for [1]+–[3]+. The paramagnetic [1]+–[3]+ show sharp1H NMR spectra with strikingly small J of 1.8–3.0 Hz. The DFT calculations on [1]+ predict that the triplet(S = 1) state exists above (1004 cm1) the singlet (S = 0) ground state. [1]+ exhibits l = 2.2 BM at 300 Kwhich diminishes to 0.3 BM near 2 K due to the steady decrease in the ratio of triplet to singlet populationwith the lowering of temperature. [1]+–[3]+ exhibit one oxidation and two successive reductions each inCH3CN. Experimental and DFT analyses collectively establish the valence configurations at thenon-innocent {Ru–Q} interface along the redox chain as [(tpm)(Cl)RuIII(QQo)]2+ ([1]2+–[3]2+)?[(tpm)(Cl)RuIII(QSq)]+ ([1]+–[3]+)?[(tpm)(Cl)RuII(QSq)]M[(tpm)(Cl)RuIII(QCat)] (1–3)?[(tpm)(Cl)-RuII(QCat)] ([1]–[3]). The spectral features of [1]n–[3]n (n = +2, +1, 0) have been addressed based onthe TD-DFT calculations on [1]n.

Place, publisher, year, edition, pages
2011. Vol. 374, 216-225 p.
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-236123DOI: 10.1016/j.ica.2011.02.079OAI: oai:DiVA.org:uu-236123DiVA: diva2:762768
Available from: 2014-11-12 Created: 2014-11-12 Last updated: 2017-12-05

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