Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment
| Autor: | Jean-Cyrille Hierso, Régine Amardeil, Julien Roger, Philippe Richard, Paul Fleurat-Lessard, Marie-José Penouilh, Vincent Rampazzi |
|---|---|
| Přispěvatelé: | Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Universitaire de France ( IUF ), Ministère de l'Éducation nationale, de l’Enseignement supérieur et de la Recherche ( M.E.N.E.S.R. ), Université de Bourgogne (MESRT Ph.D. Grant), Région Bourgogne (PART I-SMT8), Région Bourgogne (PART CNRS (3MIM)), Institut Universitaire de France, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Steric effects
basis-sets coordination-complexes Stereochemistry [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Inorganic Chemistry topological analysis chemistry.chemical_compound electron localization Cyclopentadienyl complex antitumor-activity Diphosphines molecular-orbital methods Physical and Theoretical Chemistry x-ray-structure p-31 nmr 010405 organic chemistry Ligand crystal-structure [ CHIM.INOR ] Chemical Sciences/Inorganic chemistry spin couplings 0104 chemical sciences chemistry Ferrocene Intramolecular force Metallocene Phosphine |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2016, 55 (21), pp.10907-10921. 〈http://pubs.acs.org/doi/full/10.1021/acs.inorgchem.6b01318〉. 〈10.1021/acs.inorgchem.6b01318〉 Inorganic Chemistry, American Chemical Society, 2016, 55 (21), pp.10907-10921. ⟨10.1021/acs.inorgchem.6b01318⟩ |
| ISSN: | 0020-1669 1520-510X |
| DOI: | 10.1021/acs.inorgchem.6b01318〉. |
| Popis: | International audience; A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis-(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis-(5-methy1-2-furyl)phosphino]-3,3'-di-tert-butyfferrocene (5-r), and rac-1,1'-bis ( diphenylphosphino)-3,3'-bis [(tri-iso-propylsilyl)-oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e(-) to 16e(-) gold centers coexist. In such complexes, nonbonded ("through-space") P-31-P-31' nuclear spin couplings were evidenced by high-resolution NMR In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a sigma covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu center dot center dot center dot AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au center dot center dot center dot Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|