Polynuclear manganese complexes with the dicarboxylate ligand m-phenylenedipropionate:: A hexanuclear mixed-valence (3MnIII, 3MnIV) complex

被引:56
作者
Cañada-Vilalta, C
Streib, WE
Huffman, JC
O'Brien, TA
Davidson, ER
Christou, G [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
[2] Indiana Univ, Ctr Mol Struct, Bloomington, IN 47405 USA
[3] Indiana Univ Purdue Univ, Dept Chem, Indianapolis, IN 46202 USA
[4] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
关键词
D O I
10.1021/ic034973m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dicarboxylate group m-phenylenedipropionate (mpdp(2-)) has been used for the synthesis of four new Mn compounds of different nuclearities and oxidation states: [Mn2O(mpdp)(bpy)(2)(H2O)(MeCN)](ClO4)(2) (3), [Mn3O(mpdp)(3)(py)(3)](ClO4) (4), [Mn3O(mpdp)(3)(py)(3)] (5), and [Mn6O7(mpdp)(3)(bpy)(3)](ClO4) (6). Compound 3 (2Mn(III)) contains a [Mn-2(mu-O)](4+) core, whereas 5 (Mn-II 2Mn(III)) and 4 (3Mn(III)) contain the [Mn-3(mu(3)-O)](6+,7+) core, respectively. In all three compounds, the mpdp(2-) ligand is flexible enough to adopt the sites occupied by two monocarboxylates in structurally related compounds, without noticeable distortion of the cores. Variable-temperature magnetic susceptibility studies establish that 3 and 5 have ground-state spin values of S = 0 and S = 1/2, respectively. Compound 6 is a highly unusual 3Mn(III), 3Mn(IV) trapped-valent compound, and it is also a new structural type, with six Mn atoms disposed in a distorted trigonal antiprismatic topology. Its electronic structure has been explored by variable-temperature measurements of its dc magnetic susceptibility, magnetization vs field response, and EPR spectrum. The magnetic data indicate that it possesses an S = 3/2 ground state with an axial zero-field splitting parameter of D = -0.79 cm(-1), and this conclusion is supported by the EPR data. The combined results demonstrate the ligating flexibility of the mpdp(2-) ligand and its usefulness in the synthesis of a variety of Mn-x species.
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页码:101 / 115
页数:15
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