Synthesis and Characterization of Di- and Trivalent Pyrazolylborate 尾-Diketonates and Cyanometalates

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• 作者：Minao Tang ; Dongfeng Li ; Uma Prasad Mallik ; Yuan-Zhu Zhang ; Rodolphe Cle虂rac ; Gordon T. Yee ; Myung-Hwan Whangbo ; Amshumali Mungalimane ; Stephen M. Holmes
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：June 6, 2011
• 年：2011
• 卷：50
• 期：11
• 页码：5153-5164
• 全文大小：1045K
• 年卷期：v.50,no.11(June 6, 2011)
• ISSN：1520-510X

文摘

The syntheses, structures, and magnetic properties of a series of di- and trivalent hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) cyanomanganates are described. Treatment of tris(acetylacetonate)manganese(III) [Mn(acac)₃] with KTp* and tetra(ethyl)ammonium cyanide affords [NEt₄][(Tp*)Mn^II(魏²-acac)(CN)] (1), as the first monocyanomanganate(II) complex; attempted oxidation of 1 with iodine affords {(Tp*)Mn^II(魏²-acac^3-CN)}_n (2) as a one-dimensional chain and bimetallic {[NEt₄][(Tp*)Mn^II(魏²-acac^3-CN)]₂(渭-CN) (3) as the major and minor products, respectively. A fourth complex, [NEt₄][(Tp*)Mn^II(畏²-acac^3-CN)(畏¹-NC-acac)] (4), is obtained via treatment of Mn(acac^3-CN)₃ with KTp* and [NEt₄]CN, while [NEt₄]₂[Mn^II(CN)₄] (5) was prepared from manganese(II) trifluoromethanesulfonate and excess [NEt₄]CN. Tricyanomanganate(III) complexes, [cat][(Tp*)Mn^III(CN)₃] [cat = NEt₄⁺, 7; PPN⁺, 8], are prepared via sequential treatment of Mn(acac^3-CN)₃ with KTp*, followed by [NEt₄]CN, or [cat]₃[Mn^III(CN)₆] with (Tp*)SnBu₂Cl. Magnetic measurements indicate that 1, 2, and 4 contain isotropic Mn^II (S = ⁵/₂; g = 2.00) centers, and no long-range magnetic ordering is found above 1.8 K. Compounds 7 and 8 contain S = 1 Mn^III centers that adopt singly degenerate spin ground states without orbital contributions to their magnetic moments.