Heteroatomic Molecular Clusters Derived from Group 15 Zintl Ion Cages: Synthesis and Isolation of [M2(HP7)2]2鈭?/sup> (M = Ag, Au), Two Novel Cluster Anions Exhibi

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• 作者：Caroline M. Knapp ; Charlotte S. Jackson ; Joseph S. Large ; Amber L. Thompson ; Jose M. Goicoechea
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 2, 2011
• 年：2011
• 卷：50
• 期：9
• 页码：4021-4028
• 全文大小：859K
• 年卷期：v.50,no.9(May 2, 2011)
• ISSN：1520-510X

文摘

Ethylenediamine (en) solutions of K₃P₇ and 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) were reacted with the homoleptic group 11 complexes [M(nbe)₃][SbF₆] (M = Ag, Au; nbe = norbornene) yielding two novel cluster anions, [M₂(HP₇)₂]^{2鈭?/sup>, both of which were isolated in low crystalline yields as [K(2,2,2-crypt)]₂[M₂(HP₇)₂] (M = Ag (1) and Au (2)). Optimization of the reaction conditions by incorporation of a proton source (ammonium tetraphenylborate) and the replacement of the light-sensitive nbe adducts of silver and gold with the chloride salts MCl (M = Ag, Au) was found to greatly increase the yield and purity in which 1 and 2 were isolated. Compounds 1 and 2 were characterized by single crystal X-ray diffraction, electrospray ionization mass-spectrometry (ESI鈭?MS), elemental analysis, and 1H and 31P NMR spectroscopy. Density functional theory (DFT) calculations on the cluster anions were also conducted.}