Novel Types of Tetra-, Hexa-, Octa-, and Dodecanuclear Silver Clusters Containing (2,7-Di-tert-butylfluoren-9-ylidene)methanedithiolate†

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• 作者：Jos Vicente^‡ ; ; Pablo Gonzlez-Herrero*^‡ ; ; Yolanda Garca-Snchez^‡ ; ; Peter G. Jones^§ ;
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：March 2, 2009
• 年：2009
• 卷：48
• 期：5
• 页码：2060-2071
• 全文大小：381K
• 年卷期：v.48,no.5(March 2, 2009)
• ISSN：1520-510X

文摘

The reaction of AgClO₄ with piperidinium 2,7-di-tert-butyl-9H-fluorene-9-carbodithioate (pipH)[S₂C(t-Bu-Hfy)] (1) (t-Bu-Hfy = 2,7-di-tert-butylfluoren-9-yl) afforded [Ag_n{S₂C(t-Bu-Hfy)}_n] (2), which reacted with phosphines to give [Ag{S₂C(t-Bu-Hfy)}L₂] [L = PPh₃ (3a); L₂ = bis(diphenylphosphino)ethane (dppe, 3b), 1,1′-bis(diphenylphosphino)ferrocene (dppf, 3c). By reacting complex 2 with AgClO₄ and piperidine in a 1:1:1 molar ratio, the dodecanuclear cluster [Ag₁₂{S₂C(t-Bu-fy)}₆] (4) (t-Bu-fy = 2,7-di-tert-butylfluoren-9-ylidene) was obtained. Compound 4 can also be directly prepared from the reaction of 1 with AgClO₄ and piperidine in a 1:2:1 molar ratio. The reactions of 1 with AgClO₄, phosphines, and piperidine afforded the compounds [Ag₆{S₂C(t-Bu-fy)}₃L₅] [1:2:2:1 molar ratio; L = PPh₃ (5a), P(p-To)₃ (5b)], [Ag₄{S₂C(t-Bu-fy)}₂(dppf)₂] (6) (1:2:1:1 molar ratio), [Ag_n{S₂C(t-Bu-fy)}_n/2{P(i-Pr)₃}_n] (7) (1:2:2:1 molar ratio), or [Ag₈{S₂C(t-Bu-fy)}₄{P(i-Pr)₃}₄] (8) (1:2:1:1 molar ratio). Complexes 5a,b, 6, 7, and 8 can be also obtained by reacting 4 with the corresponding phosphine in the appropriate molar ratio. The crystal structures of 4, 5b, and 8 have been determined by X-ray diffraction studies. The nuclearity of complex 6 was established from its ³¹P{¹H} NMR data, which reveal a very fast dynamic process leading to an average coupling of each of the P atoms of the dppf ligands with four Ag atoms.