Titre du document / Document title

Unusual Ar-H/Rh-H J_HH NMR coupling in complexes of Rhodium(III): Experimental evidence and theoretical support for an η¹-arene structure

Auteur(s) / Author(s)

KRUMPER Jennifer R. ⁽¹⁾ ; GERISCH Michael ⁽¹⁾ ; MAGISTRATO Alessandra ⁽²⁾ ; ROTHLISBERGER Ursula ⁽³⁾ ; BERGMAN Robert G. ⁽¹⁾ ; TILLEY T. Don ⁽¹⁾ ;

Affiliation(s) du ou des auteurs / Author(s) Affiliation(s)

⁽¹⁾ Department of Chemistry, University of California and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94702, ETATS-UNIS
⁽²⁾ International School for Advanced Studies (ISAS/SISSA) and INFM-Democritos Center, Trieste 34140, ITALIE
⁽³⁾ Laboratory of Computational Chemistry & Biochemistry, BCH 4109 EPFL, Lausanne 1015, SUISSE

Résumé / Abstract

The synthesis and structural properties of three new hydridorhodium(III) complexes are reported. Hydrogenolysis of the cyclometalated rhodium dichloride complexes [RhCl₂{(S,S)-benbox(Me2)}] (2a-c) leads to formation of the new complexes [RhCl₂(H){(S,S)-ip-benbox(Me2)H}] (3a-c) in 45% to 85% yield. Compounds 3a-c were found to have unusual features by NMR spectroscopy: in particular, downfield shifted aryl proton resonances (8.88-9.03 ppm) that were coupled to the rhodium hydride resonances. Using X-ray crystallographic studies, a variety of solid- and solution-state characterization techniques, and DFT calculations, these features were attributed to the presence of weak π-type η¹-arene interactions in 3a-c.

Revue / Journal Title

Journal of the American Chemical Society   ISSN 0002-7863   CODEN JACSAT 

Source / Source

2004, vol. 126, n^o39, pp. 12492-12502 [11 page(s) (article)] (99 ref.)

Langue / Language

Anglais

Editeur / Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1879) (Revue)

Mots-clés anglais / English Keywords

Platinoid Complexes ; Transition metal Complexes ; X ray diffraction ; NMR spectrometry ; Homonuclear correlation ; Two dimension spectrometry ; Molecular interaction ; Electronic structure ; Crystalline structure ; Molecular structure ; Organic ligand ; Hydrido complex ; Chloro complex ; Rhodium Complexes ; Inorganic synthesis ;

Mots-clés français / French Keywords

Platinoïde Complexe ; Métal transition Complexe ; Benzène(1,3-bis[(4,4-dialkyl)oxazolin-2-yl]méthyl-4,6-diméthyl) ; Diffraction RX ; Spectrométrie RMN ; Corrélation homonucléaire ; Spectrométrie 2 dimensions ; Interaction moléculaire ; Structure électronique ; Structure cristalline ; Structure moléculaire ; Coordinat organique ; Complexe hydruro ; Complexe chloro ; Rhodium Complexe ; Synthèse minérale ;

Mots-clés espagnols / Spanish Keywords

Platinoide Complejo ; Metal transición Complejo ; Difracción RX ; Espectrometría RMN ; Correlación homonuclear ; Espectrometría bidimensional ; Interacción molecular ; Estructura electrónica ; Estructura cristalina ; Estructura molecular ; Ligando orgánico ; Complejo hidruro ; Complejo cloro ; Rodio Complejo ; Síntesis inorgánica ;

Localisation / Location

INIST-CNRS, Cote INIST : 551, 35400012239928.0700