Exceptionally Long (≥2.9 Å) C-C Bonds between [TCNE]- Ions: Two-Electron, Four-Center π*-π* C-C Bonding in π-[TCNE]22

Juan J Novoa; Pilar Lafuente; Rico E Del Sesto; Joel S Miller

doi:10.1002/1521-3773(20010702)40:13<2540::AID-ANIE2540>3.0.CO;2-O

Exceptionally Long (≥2.9 Å) C-C Bonds between [TCNE]^- Ions: Two-Electron, Four-Center π-π C-C Bonding in π-[TCNE]₂²

Angew Chem Int Ed Engl. 2001 Jul 2;40(13):2540-2545. doi: 10.1002/1521-3773(20010702)40:13<2540::AID-ANIE2540>3.0.CO;2-O.

Authors

Juan J Novoa¹, Pilar Lafuente¹, Rico E Del Sesto², Joel S Miller²

Affiliations

¹ Department of Physical Chemistry University of Barcelona Av. Diagonal, 647, 08028 Barcelona (Spain) Fax: (+34) 93-402-1231.
² Prof. J. S. Miller, R. E. Del Sesto Department of Chemistry University of Utah Salt Lake City, UT, 84112 (USA) Fax: (+1) 801-581-8433.

PMID: 29712282
DOI: 10.1002/1521-3773(20010702)40:13<2540::AID-ANIE2540>3.0.CO;2-O

Abstract

Attractive interaction with the cation overcomes the electrostatic repulsion between two tetracyanoethylene radical anions, [TCNE]^.- , and leads to the formation of a diamagnetic dimer [TCNE]₂^2- , for example, in [K(glyme)]₂ [TCNE]₂ . The bonding is described as two-electron, four-center bonding arising from π*-π* overlap. Crystallographic as well as spectroscopic (IR and UV/Vis) features of this bonding are observed.

Keywords: pi*-pi* bonding; radical ions; self-assembly; supramolecular interactions; tetracyanoethylene.