Gold(I) Chloride Complexes of Polyphosphine Ligands with Electron-Rich Arene Spacer: Gold鈥揂rene Interactions

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• 作者：Qing-Ling Ni ; Xuan-Feng Jiang ; Ting-Hong Huang ; Xiu-Jian Wang ; Liu-Cheng Gui ; Kun-Guo Yang
• 刊名：Organometallics
• 出版年：2012
• 出版时间：March 26, 2012
• 年：2012
• 卷：31
• 期：6
• 页码：2343-2348
• 全文大小：284K
• 年卷期：v.31,no.6(March 26, 2012)
• ISSN：1520-6041

文摘

The reactions of Au(tht)Cl (tht = tetrahydrothiophene) with the electron-rich-arene-spacer-containing polyphosphine ligands N,N鈥?bis((diphenylphosphino)methyl)benzene-1,4-diamine (Dpba), N,N鈥?bis((diphenylphosphino)methyl)naphthalene-1,5-diamine (Dpna), N,N,N鈥?N鈥? tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine (Pbaa), N,N,N鈥?N鈥?tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine (Pnaa), and N,N,N鈥?N鈥?tetrakis((diphenylphosphino)methyl)biphenyl-4,4鈥?diamine (Pbbaa) lead to [Dpba(AuCl)₂] (1), [Dpna(AuCl)₂] (2), [Pnaa(AuCl)₄] (3), [Pbbaa(AuCl)₄ (4). and [Pbaa(AuCl)₄] (5), which are characterized by ¹H and ³¹P NMR, IR, elemental analysis, and X-ray crystal structure analysis. These complexes exhibit weak Au鈥揳rene interactions with the electron-rich arene spacer, while the Au鈥揳rene interactions are modified by a combination of electronic and steric effects from the ligands. Different from monomeric complexes 1, 2, 3, and 4, complex 5 in the solid state exhibits a centrosymmetric trimeric unit that is constructed by intermolecular Au路路路Au interactions between the central molecule and the two symmetry-related terminal molecules and in which the conformation of the central molecule is different from that of the two symmetric terminal molecules. On the basis of the Kochi鈥檚 geometric criteria and the crystal structural parameters relating to Au鈥揳rene interactions, the Au路路路C_arene contacts in 3 and 4 feature nearly 畏²-arene interactions, while the Au路路路C_arene contacts in 5 can be described as 畏¹-arene interactions, and the Au路路路C_arene contacts in 1 and 2 are very weak due to intermolecular N鈥揌路路路Cl interactions.