A REMARKABLE FAMILY OF RHODIUM ACETONITRILE COMPOUNDS SPANNING THREE OXIDATION STATES AND WITH NUCLEARITIES RANGING FROM MONONUCLEAR AND DINUCLEAR TO ONE-DIMENSIONAL CHAINS
A REMARKABLE FAMILY OF RHODIUM ACETONITRILE COMPOUNDS SPANNING THREE OXIDATION STATES AND WITH NUCLEARITIES RANGING FROM MONONUCLEAR AND DINUCLEAR TO ONE-DIMENSIONAL CHAINS
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跨越三个氧化态、核范围从单核、双核到一维链的一类卓越的乙腈铑化合物
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
K. Dunbar
中科院分区：
文献类型：
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作者：
M. Prater;Laura E. Pence;R. Clérac;Gary M. Finniss;C. Campana;P. Auban;D. Jérome;E. Canadell;K. Dunbar
合成了一系列 Rh(I,II)、Rh(II) 和 Rh(III) 均配阳离子，并在固态和溶液中进行了表征。通过在乙腈或丙腈中用 Et3OBF4 或 Me3Si(CF3SO3) 处理 Rh2(O2CCH3)4(L)2 制备了三种新的二铑(II,II)双核化合物。 [Rh2II,II(MeCN)10][BF4]4 (1)、[Rh2II,II(MeCN)10][SO3CF3]4 (2) 和 [Rh2II,II(EtCN)10][BF4]4 (3) 中的阳离子包含八个赤道 RCN 基团，围绕两个 Rh 原子和两个轴向 RCN 分子以近似方形平面排列。通过循环伏安法研究了 1−3 的氧化还原性质，结果表明存在一两个不可逆还原，但没有氧化。尽管没有电化学证据证明可进行氧化，但发现用 NOBF4 处理 [Rh2II,II(MeCN)10][BF4]4 会产生均配乙腈家族的另一个成员，即八面体 d6 阳离子 [RhIII(MeCN)6][BF4]3，(4)。相应的一电子还原...
A series of homoleptic cations of Rh(I,II), Rh(II), and Rh(III) have been synthesized and characterized in the solid-state and in solution. Three new dinuclear compounds of dirhodium(II,II) were prepared by treatment of Rh2(O2CCH3)4(L)2 with Et3OBF4 or Me3Si(CF3SO3) in acetonitrile or propionitrile. The cations in [Rh2II,II(MeCN)10][BF4]4 (1), [Rh2II,II(MeCN)10][SO3CF3]4 (2), and [Rh2II,II(EtCN)10][BF4]4 (3) contain eight equatorial RCN groups oriented in an approximately square planar arrangement around the two Rh atoms and two axial RCN molecules. The redox properties of 1−3 were investigated by cyclic voltammetry, which revealed the presence of one or two irreversible reduction(s) but no oxidations. Although there was no electrochemical evidence for an accessible oxidation, it was found that treatment of [Rh2II,II(MeCN)10][BF4]4 with NOBF4 occurs to yield another member of the homoleptic acetonitrile family, namely, the octahedral d6 cation [RhIII(MeCN)6][BF4]3, (4). The corresponding one-electron redu...