Synthesis and Characterization of Di- and Trivalent Pyrazolylborate β-Diketonates and Cyanometalates - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2011

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

Résumé

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*)MnII(κ2- acac)(CN)] (1), as the first monocyanomanganate(II) complex; attempted oxidation of 1 with iodine affords {(Tp*)MnII(κ2-acac3-CN)}n(2) as a one-dimensional chain and bimetallic {[NEt4]- [(Tp*)MnII(κ2-acac3-CN)]2(μ-CN) (3) as the major and minor products, respectively. A fourth complex, [NEt4][(Tp*)MnII (η2-acac3-CN)(η1-NC-acac)] (4), is obtained via treatment of Mn- (acac3-CN)3 with KTp* and [NEt4]CN, while [NEt4]2- [MnII(CN)4] (5) was prepared from manganese(II) trifluoromethanesulfonate and excess [NEt4]CN. Tricyanomanganate(III) complexes, [cat][(Tp*)MnIII(CN)3] [cat = NEt4 þ, 7; PPNþ,8], are prepared via sequential treatment of Mn(acac3-CN)3 with KTp*, followed by [NEt4]CN, or [cat]3[MnIII(CN)6] with (Tp*)SnBu2Cl. Magnetic measurements indicate that 1, 2, and 4 contain isotropic MnII (S = 5/2; g = 2.00) centers, and no longrange magnetic ordering is found above 1.8 K. Compounds 7 and 8 contain S = 1 MnIII centers that adopt singly degenerate spin ground states without orbital contributions to their magnetic moments.

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Matériaux
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Dates et versions

hal-00611163 , version 1 (25-07-2011)

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Minao Tang, Dongfeng Li, Uma Prasad Mallik, Yuan-Zhu Zhang, Rodolphe Clérac, et al.. Synthesis and Characterization of Di- and Trivalent Pyrazolylborate β-Diketonates and Cyanometalates. Inorganic Chemistry, 2011, 50, pp. 5153-5164. ⟨10.1021/ic200464t⟩. ⟨hal-00611163⟩

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