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

0433941 - ÚFCH JH 2015 RIV NL eng J - Journal Article
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
R&D Projects: GA MŠMT LD14129
Institutional support: RVO:61388955
Keywords : Transition metal complex * Density functional theory * Potential energy surface
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.046, year: 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.
Permanent Link: http://hdl.handle.net/11104/0238105