Amine-Amide Equilibrium in Gold(III) Complexes and a Gold(III)-Gold(I) Aurophilic Bond

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• 作者：Lingyun Cao ; Michael C. Jennings ; Richard J. Puddephatt
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：February 19, 2007
• 年：2007
• 卷：46
• 期：4
• 页码：1361 - 1368
• 全文大小：202K
• 年卷期：v.46,no.4(February 19, 2007)
• ISSN：1520-510X

文摘

The ligands HN(CH₂-2-C₅H₄N)₂, BPMA, and PhCH₂N(CH₂-2-C₅H₄N)₂, BBPMA, react with Na[AuCl₄] to give thecationic complexes [AuCl(BPMA-H)]⁺ and [AuCl(BBPMA)]²⁺, respectively. The amido complex [AuCl(BPMA-H)]⁺undergoes easy inversion at the amido nitrogen atom and can be reversibly protonated by triflic acid to give[AuCl(BPMA)]²⁺. The complex [AuCl(BBPMA)]²⁺ is easily decomposed in aqueous solution by cleavage of a carbon-nitrogen bond or, in dilute HCl solution, by protonation of the ligand to give [BBPMAH₂]Cl[AuCl₄] The complexes[BBPMAH₂]Cl[AuCl₄] and [BBPMAH₂]Cl[AuCl₂] can be formed by direct reaction of BBPMA with H[AuCl₄]. Unusualforms of gold(III)···gold(III) and gold(III)···gold(I) aurophilic bonding are observed in the salts [AuCl(BPMA-H)][PF₆] and [AuCl(BPMA-H)][AuCl₂], respectively. The first comparison of the structures of gold(III) amine and amidocomplexes, in the cations [AuCl(BPMA-H)]⁺ and [AuCl(BPMA)]²⁺, indicates that there is little p-d bonding in theamido-gold bond and that the amide exerts a stronger trans influence than the amine group.