Structural flexibility of 2-hetaryl chromium aminocarbene complexes: Experimental and theoretical evidence

0433941 - ÚFCH JH 2015 RIV NL eng J - Článek v odborném periodiku
Kvapilová, Hana - Eigner, V. - Hoskovcová, I. - Tobrman, T. - Čejka, J. - Záliš, Stanislav
Structural flexibility of 2-hetaryl chromium aminocarbene complexes: Experimental and theoretical evidence.
Inorganica chimica acta. Roč. 421, SEP 2014 (2014), s. 439-445. ISSN 0020-1693. E-ISSN 1873-3255
Grant CEP: GA MŠMT LD14129
Institucionální podpora: RVO:61388955
Klíčová slova: Transition metal complex * Density functional theory * Potential energy surface
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.046, rok: 2014

Chromium aminocarbene complexes [(CO)(5)Cr = C(N(CH3)(2))R], R = N-methyl-2-pyrrolyl, 2-thienyl and 2-furyl were prepared and structurally characterized. X-ray study indicated two stable rotamers in case of compounds containing 2-thienyl and 2-furyl substituents. DFT calculations well interpreted structural parameters of all studied complexes. Calculations of potential energy surfaces (PES) for neutral species confirmed existence of two energy minima on the potential energy surfaces. Calculated rotation barriers increase in the series 2-furyl, 2-thienyl and N-methyl-2-pyrrolyl, respectively. The PES scans for compounds in one-electron reduced states essentially reveal opposite behavior to the one observed for neutral complexes. Connection is drawn between the observed structural flexibility and electrochemical properties of the compounds. (C) 2014 Elsevier B.V. All rights reserved.
Trvalý link: http://hdl.handle.net/11104/0238105