Cyclometallated Rhodium(III) Complexes with Diimine Ligands
Cyclometallated Rhodium(III) Complexes with Diimine Ligands
复制标题
环金属铑 (III) 与二亚胺配体的配合物
DOI：
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发表时间：
1986
期刊：
影响因子：
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通讯作者：
T. Jenny
中科院分区：
文献类型：
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作者：
U. Mäder;A. V. Zelewsky;T. Jenny
描述了单核 Rh(III) 络合物的合成，作为一系列相关物质的代表性例子，该络合物包含来自双核 Cl-桥化合物的两个环金属化配体 ppy (2-苯基吡啶) 和一个二亚胺 bpy (2,2'-联吡啶)。吸收光谱在 364 nm (e = 7000) 处显示最大值，在 454 nm 处有非常弱的肩峰 (e = 10)。该带暂时分配给金属到配体的电荷转移跃迁。在循环伏安图中，在 E1/2 = -1.41 V（相对于 NHE）处出现可逆单电子还原，在 Ep = + 1.1 V 处出现不可逆氧化。详细的 NMR 分析（包括 13C-NMR、NOE、SFORD 以及 bpy 配体的氘化）表明仅形成一种异构体，具有 C2 轴，将 bpy 配体与两个碳配体一分为二处于顺式位置。观察到 103Rh、13C 和 103Rh,H 偶联。
The synthesis of a mononuclear Rh(III) complex, as a representative example of a series of related species, containing two cyclometallating ligands ppy (2-phenylpyridine) and one diimine bpy (2,2′-bipyridine) from a binuclear Cl-bridged compound is described. The absorption spectrum shows a maximum at 364 nm (e = 7000), with a very weak shoulder (e = 10) at 454 nm. This band is tentatively assigned to a metal-to-ligand charge-transfer transition. A reversible, one-electron reduction appears in the cyclic voltammogram at E1/2 = −1.41 V (vs. NHE) and a irreversible oxydation at Ep = + 1.1 V. A detailed NMR analysis including 13C-NMR, NOE, SFORD as well as deuteration of the bpy ligand indicates the formation of only one isomer, having a C2 axis, bisecting the bpy ligand, with the two carbon ligands in cis-position. 103Rh, 13C and 103Rh,H couplings are observed.