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

详细信息    查看全文

• 作者：Julien Dubarle-Offner ; Marion Barbazanges ; Myl猫ne Aug茅 ; Christophe Desmarets ; Jamal Moussa ; M. Rosa Axet ; Cyril Ollivier ; Corinne Aubert ; Louis Fensterbank ; Vincent Gandon ; Max Malacria ; Geoffrey Gontard ; Hani Amouri
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 25, 2013
• 年：2013
• 卷：32
• 期：6
• 页码：1665-1673
• 全文大小：477K
• 年卷期：v.32,no.6(March 25, 2013)
• ISSN：1520-6041

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.