Titre du document / Document title

Synthesis and reactivity of the hydrido- and alkylrhenium methylidene complexes Cp*(PMe₃)₂(R)Re=CH₂ (R = H, CH₃)

Auteur(s) / Author(s)

KRUMPER Jennifer R. ⁽¹⁾ ; MARTIN Richard L. ⁽²⁾ ; HAY P. Jeffrey ⁽²⁾ ; YUNG Cathleen M. ⁽¹⁾ ; VELTHEER John ⁽¹⁾ ; BERGMAN Robert G. ⁽¹⁾ ;

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

⁽¹⁾ Theoretical Division, Los Alamos National Laboratory, Mail Stop B268, Los Alamos, New Mexico 87545, ETATS-UNIS
⁽²⁾ Department of Chemistry, University of California, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94702, ETATS-UNIS

Résumé / Abstract

Protonolysis of the dimethylrhenium(III) compound Cp*(PMe₃)₂Re(CH₃)₂ (3) led to formation of the highly reactive hydridorhenium methylidene compound [Cp*(PMe3)2Re(CH2)(H)][OTf] (4), which was characterized spectroscopically at low temperature. Although 4 decomposed above -30 °C, reactivity studies performed at low temperature indicated it was in equilibrium with the coordinatively unsaturated methylrhenium complex [Cp*(PMe3)2Re(CH3)][OTf] (2). Methylidene complex 4 was found to react with PMe₃ to afford [Cp*(PMe₃)₃Re(CH3)][OTf] (6) and with chloride anion to give Cp*(PMe₃)₂Re(Me)Cl (7). When BAr_f anion was added to 4, the thermally stable methylrhenium methylidene complex [Cp*(PMe₃)₂-Re(CH₂)(CH₃)][BAr_i] (8) was isolated upon warming to room temperature. The mechanisms of formation of both 4 and 8 are discussed in detail, including DFT calculations. The novel carbonyl ligated complex Cp*-(CO)₂Re(CH₃)OTf (12) was prepared, isolated, and found to not undergo migration reactions to form methylidene complexes.

Revue / Journal Title

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

Source / Source

2004, vol. 126, n^o45, pp. 14804-14815 [12 page(s) (article)] (95 ref.)

Langue / Language

Anglais

Editeur / Publisher

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

Mots-clés anglais / English Keywords

Transition metal Complexes ; Rhenium Organic compounds ; X ray diffraction ; Electronic structure ; Crystalline structure ; Molecular structure ; Chemical reactivity ; Tertiary phosphine ; Organic ligand ; Ylidene complex ; Hydrido complex ; Cationic complex ; Organic synthesis ;

Mots-clés français / French Keywords

Métal transition Complexe ; Rhénium Composé organique ; Phosphine(triméthyl) ; Rhénium(η⁵-pentaméthylcyclopentadiényl) complexe ; Diffraction RX ; Structure électronique ; Structure cristalline ; Structure moléculaire ; Réactivité chimique ; Phosphine tertiaire ; Coordinat organique ; Complexe ylidène ; Complexe hydruro ; Complexe cationique ; Synthèse organique ;

Mots-clés espagnols / Spanish Keywords

Metal transición Complejo ; Renio Compuesto orgánico ; Difracción RX ; Estructura electrónica ; Estructura cristalina ; Estructura molecular ; Reactividad química ; Fosfina terciaria ; Ligando orgánico ; Complejo ilideno ; Complejo hidruro ; Complejo catiónico ; Síntesis orgánica ;

Localisation / Location

INIST-CNRS, Cote INIST : 551, 35400012265345.0390