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

• Published in: Organometallics 2013-03, Vol.32 (6), p.1665-1673
• Main Authors: Dubarle-Offner, Julien, Barbazanges, Marion, Augé, Mylène, Desmarets, Christophe, Moussa, Jamal, Axet, M. Rosa, Ollivier, Cyril, Aubert, Corinne, Fensterbank, Louis, Gandon, Vincent, Malacria, Max, Gontard, Geoffrey, Amouri, Hani
• Format: Article
• Language: English
• Subjects: Catalysis; Chemical Sciences; Coordination chemistry
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om301101z

A novel series of π-complexes of phosphino ligands, [Cp*Ru(η 6 -arene-PAr2)][OTf], has been prepared in which the diarylphosphine unit is attached to a metalated π-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(η6-p-CH3C6H4-P(p-tol)2-Au-Cl)][OTf] and [Cp*Ru(η 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(η 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.