DFT‐Supported Threshold Ionization Study of Chromium Biphenyl Complexes: Unveiling the Mechanisms of Substituent Influence on Redox Properties of Sandwich Compounds. Issue 55 (9th August 2017)

• Record Type: Journal Article
• Authors: Ketkov, Sergey Yu.; Tzeng, Sheng‐Yuan; Wu, Pei‐Ying; Markin, Gennady V.; Tzeng, Wen‐Bih
• Is Part Of: Chemistry. Volume 23:Issue 55(2017)
• Page Start: 13669
• Page End: 13675
• Publication Date: 2017-08-09
• Subjects: DFT calculations -- ionization potentials -- MATI spectroscopy -- sandwich complexes -- substituent effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201702226
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: High‐resolution mass‐analyzed threshold ionization (MATI) spectra of (η 6 ‐Ph2 )2 Cr and (η 6 ‐Ph2 )(η 6 ‐PhMe)Cr demonstrate that the Ph groups work as electron donors, decreasing the ionization energy of the gas‐phase bisarene complexes. In contrast to electrochemical data, a close similarity of the Ph and Me group effects on the oxidation of free sandwich molecules has been revealed. However, DFT calculations testify for the opposite shifts of the electron density caused by the Me and Ph substituents in the neutral complexes, the latter behaving as an electron‐accepting fragment. On the contrary, in the bisarene cations, the Ph group becomes a stronger donor than methyl. This change provides the similar substituent effects observed with the MATI experiment. On the other hand, the well‐documented opposite influence of the Me and Ph fragments on the redox potential of the (η 6 ‐arene)2 Cr +/0 couple in solution appears to be a result of solvation effects but not intramolecular interactions as shown for the first time in this work. Abstract : Precise ionization potentials : High‐resolution mass‐analyzed threshold ionization (MATI) spectra reveal a similar decrease in the (η 6 ‐arene)2 Cr gas‐phase ionization energy (IE) by the Ph and Me substituents. DFT provides, however, quite different mechanisms of the substituent influence. On the other hand, the positive shift of the solution‐phase redox potential on going from (η 6 ‐PhH)2 Cr +/0 to (η 6 ‐Ph2 )2 Cr +/0 appears to be a result of solvation effects but not intramolecular interactions.