title: Distortions of π-coordinated arenes with anionic character.
abstract: A qualitative analysis of the distortions that operate on the π system of bridging arenes with anionic character is presented and substantiated by computational studies at the density functional B3LYP and CASSCF levels. The observed effects of bonding to two metal atoms and of the negative charge are an expansion of the arene ring due to the partial occupation of π* orbitals, an elongation or compression distortion accompanied by a loss of the equivalence of carbon-carbon bonds due to a Jahn-Teller distortion of the arene dianions, and a ring puckering due to a second-order Jahn-Teller distortion that may appear independently of the existence of the first-order effect. The workings of the orbital mixing produced by these distortions have been revealed in a straightforward way by a pseudosymmetry analysis of the HOMOs of the distorted conformations. The systems studied include Li(I) and Y(III) adducts of benzene, as well as trimethylsilyl-substituted derivatives in the former case. An analysis of the structural data of a variety of purported di- and tetraanionic arene ligands coordinated to transition metals in several bridging modes has reproduced the main geometrical trends found in the computational study for the benzene and trimethylsilyl-substituted benzene dianions, allowing a classification of the variety of structural motifs found in the literature.
authors.affiliation: Departament de Química Inorgànica and Institut de Química, Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martí i Franquès, 1-11, 08028 Barcelona (Spain).
authors.forename: Andrés
authors.initials: A
authors.lastname: Falceto
authors.forename: David
authors.initials: D
authors.lastname: Casanova
authors.forename: Pere
authors.initials: P
authors.lastname: Alemany
authors.forename: Santiago
authors.initials: S
authors.lastname: Alvarez
keywords: CASSCF calculations; Jahn-Teller distortion; benzene dianion; bridging ligands; pseudosymmetry; second-order Jahn-Teller effect