Characterization of A New Copper(I)−Nitrito Complex That Evolves Nitric Oxide

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• 作者：Wan-Jung Chuang ; I-Jung Lin ; Hsing-Yin Chen ; Yu-Lun Chang ; Sodio C. N. Hsu
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：June 21, 2010
• 年：2010
• 卷：49
• 期：12
• 页码：5377-5384
• 全文大小：867K
• 年卷期：v.49,no.12(June 21, 2010)
• ISSN：1520-510X

文摘

The complexes [Cu(κ²-Ph₂PC₆H₄(o-OMe))₂(CH₃CN)](BF₄) (1) and [CuCl(Ph₂PC₆H₄(o-OMe))₂] (2) have been prepared by treating [Cu(CH₃CN)₄](BF₄) or CuCl with two equivalents o-(diphenylphosphino)anisole (Ph₂PC₆H₄(o-OMe)) at room temperature, respectively. The reaction of 1 and (PPN)(NO₂) in acetonitrile solution affords a neutral compound [Cu(Ph₂PC₆H₄(o-OMe))₂(ONO)] (3). In contrast to the synthesis of 3, mixing NaNO₂ and 1 in MeOH yielded a unique dicopper(I) cationic species, [((Ph₂PC₆H₄(o-OMe))₂Cu)₂(μ-NO₂)]⁺ (4) after ether/CH₂Cl₂ crystallization. The molecular structures of 1−4 have been determined by an X-ray diffraction study. The copper(I)−nitrito adduct 3 containing phosphine−ether ligands forms nitric oxide gas from the reaction with acetic acid, suggesting the first example and model compound in the asymmetric O-bound copper(I) nitrite intermediate microenvironment of copper nitrite reductases (Cu-NIRs).