Gold Compounds Anchored to a Metalated Arene Scaffold: Synthesis, X-ray Molecular Structures, and Cycloisomerization of Enyne
文摘
A novel series of 蟺-complexes of phosphino ligands, [Cp*Ru(畏6-arene-PAr2)][OTf], has been prepared in which the diarylphosphine unit is attached to a metalated 蟺-arene scaffold. These organometallic phosphino ligands display either an electron-donating methyl group (鈭扨Ar2 = 鈭扨(p-tol)2) or electron-withdrawing trifluoromethyl group (鈭扨Ar2 = 鈭扨(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(畏6-p-CH3C6H4-P(p-tol)2-Au-Cl)][OTf] and [Cp*Ru(畏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(畏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 鈭扨Ph2, 鈭扨(p-tol)2, or 鈭扨(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.