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

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Department of Chemistry & Biochemistry, University of Missouri—St. Louis, St. Louis, Missouri 63121, United States
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, United States
§ Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, 430079 Wuhan, China
CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 avenue du Dr. Albert Schweitzer, F-33600 Pessac, France
Université de Bordeaux, UPR 8641, Pessac, F-33600, France
# Department of Chemistry, Virginia Polytechnic and State University, Blacksburg, Virginia 24061, United States
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States
*E-mail: [email protected] (S.M.H.).
Cite this: Inorg. Chem. 2011, 50, 11, 5153–5164
Publication Date (Web):April 26, 2011
Copyright © 2011 American Chemical Society

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    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*)MnII2-acac)(CN)] (1), as the first monocyanomanganate(II) complex; attempted oxidation of 1 with iodine affords {(Tp*)MnII2-acac3-CN)}n (2) as a one-dimensional chain and bimetallic {[NEt4][(Tp*)MnII2-acac3-CN)]2(μ-CN) (3) as the major and minor products, respectively. A fourth complex, [NEt4][(Tp*)MnII2-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+, 7; PPN+, 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 long-range 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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    Additional magnetic (Figures S4−S10) and X-ray crystallographic (Figures S1−S3; CIF format, 15) and 710 data. This material is available free of charge via the Internet at

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