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Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment

Abstract : 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.
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https://hal-univ-bourgogne.archives-ouvertes.fr/hal-01428979
Contributeur : Icmub - Université de Bourgogne <>
Soumis le : vendredi 6 janvier 2017 - 16:51:50
Dernière modification le : dimanche 23 juin 2019 - 11:00:03

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Vincent Rampazzi, Julien Roger, Régine Amardeil, Marie-José Penouilh, Philippe Richard, et al.. Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment. Inorganic Chemistry, American Chemical Society, 2016, 55 (21), pp.10907 - 10921. ⟨10.1021/acs.inorgchem.6b01318⟩. ⟨hal-01428979⟩

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