Synthesis, Structure and Cation-Binding Properties of Some [4 + 4] Metallocyclic MO22+ (M = Mo or W) Derivatives of 9-Phenyl-2,3,7-trihydroxyfluor-6-one

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• 作者：Laura J. McCormick ; Brendan F. Abrahams ; Berin A. Boughton ; Martin J. Grannas ; Timothy A. Hudson ; Richard Robson
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 3, 2014
• 年：2014
• 卷：53
• 期：3
• 页码：1721-1728
• 全文大小：453K
• ISSN：1520-510X

文摘

The trianion Z^{3鈥?/sup> obtained from 9-phenyl 2,3,7-trihydroxyfluor-6-one, ZH₃, affords dioxomolybdenum and dioxotungsten derivatives which contain [4 + 4] metallocycles of composition [(MO₂)₄Z₄]4鈥?/sup> (M = Mo, W) in combination with a variety of counter cations. The syntheses, structures and ESMS of the following compounds are presented: compound 1, (MePPh₃)₃(NBu₄)[(MoO₂)₄Z₄]; compound 2, (MePPh₃)₃(NBu₄)[(WO₂)₄Z₄]; compound 3, (MePPh₃)₄[(WO₂)₄Z₄]; compound 4, (PPh₄)₂(NBu₄)₂[(MoO₂)₄Z₄]; compound 5, (AsPh₄)₃(NBu₄)[(MoO₂)₄Z₄]; compound 6, (AsPh₄)₂(NBu₄)₂[(WO₂)₄Z₄]; compound 7, (Ph₃PNPPh₃)(NBu₄)₃[(MoO₂)₄Z₄]; compound 8, (Ph₃PNPPh₃)(NBu₄)₃[(WO₂)₄Z₄]; compound 9, (NEt₄)(NBu₄)₃[(MoO₂)₄Z₄]. The metallocycles in all of these compounds have similar structures, with the four metal centers located at the corners of a square slightly distorted, to varying degrees, toward a rhombus and also toward a tetrahedron. Various cations are bound inside the anionic metallocycles. ESI mass spectrometry shows that the metallocycles remain intact in the gas phase, forming [(MO₂)₄Z₄]4鈥?/sup>, {X-[(MO₂)₄Z₄]}3鈥?/sup> and in some cases {X₂-[(MO₂)₄Z₄]}2鈥?/sup> where X+ is an organic cation.}