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Gold Compounds Anchored to a Metalated Arene Scaffold: Synthesis, X-ray Molecular Structures, and Cycloisomerization of Enyne

Abstract : A novel series of pi-complexes of phosphino ligands, [Cp*Ru(eta(6)-arene-PAr2)][OTf], has been prepared in which the diarylphosphine unit is attached to a metalated pi-arene scaffold. These organometallic phosphino ligands display either an electron-donating methyl group (-PAr2 = -P(p-tol)(2)) or electron-withdrawing trifluoromethyl group (-PAr2 = -P(p-C6H4CF3)(2)). This unique class of metallo ligands was converted to heterodinuclear gold complexes upon treatment with [AuCl(tht)]. The molecular structures of [Cp*Ru(eta(6)-p-CH3C6H4-P(p-tol)(2)-Au-Cl)][OTf] and [Cp*Ru(eta(6)-C6H5-P(p-C6H4CF3)(2))-Au-Cl][OTf] were ascertained by single-crystal X-ray diffraction. A comparative study of these structures with that of [Cp*Ru(eta(6)-C6H5-PPh2-Au-Cl)][OTf] previously reported revealed important information about the electronic nature of the gold center when it is bonded to a -PPh2, -P(p-tol)(2), or -P(p-C6H4CF3)(2) metallo ligand. DFT computations also shed light on the effect of [Cp*Ru+] coordination to [AuCl(PAr3)] precatalysts. Several complexes of the family with electron-donating and -withdrawing groups were evaluated toward cycloisomerization reactions of a classical N-tethered 1,6-enyne. These results are presented and discussed.
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https://hal.archives-ouvertes.fr/hal-01397904
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Submitted on : Wednesday, November 16, 2016 - 2:23:53 PM
Last modification on : Thursday, November 5, 2020 - 2:28:04 PM

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Christophe Desmarets, Jamal Moussa, M. Rosa Axet, Cyril Ollivier, Corinne Aubert, et al.. Gold Compounds Anchored to a Metalated Arene Scaffold: Synthesis, X-ray Molecular Structures, and Cycloisomerization of Enyne. Organometallics, American Chemical Society, 2013, 32 (6), pp.1665-1673. ⟨10.1021/om301101z⟩. ⟨hal-01397904⟩

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