A stable manganese(V)-oxo corrolazine complex
A stable manganese(V)-oxo corrolazine complex
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DOI：
10.1021/ja028651d
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发表时间：
2002-12-25
影响因子：
15
通讯作者：
Goldberg, DP
中科院分区：
文献类型：
--
作者：
Mandimutsira, BS;Ramdhanie, B;Goldberg, DP
报道了氧锰(V)腐蚀嗪（TBP）8(Cz)Mn(V) oro(2)的合成和表征。这种非常稳定的高价配合物是由（TBP）8(Cz)Mn(III)(1)与- cpba的化学计量反应得到的，在室温下很容易用标准色谱方法在硅胶上纯化。配合物2的抗磁1h NMR谱显示为低自旋d2Mn(V)；2的LDI-TOFMS显示了预测的同位素包线atm/z1426.8。在末端氧基与H218O交换后，这个包络层会像预期的那样转移到更高的质量。无论是在溶液中还是在固态中，2的共振拉曼光谱都显示出Mn−氧键的拉伸模式的拉曼带的强烈增强，并且在18o取代时也发生了预期的位移：2(16O), 979 cm-1；2(18O), 938 cm-1（CH2Cl2）。最初的反应性研究表明，2将末端的氧配体迅速转移到PPh3上，导致opph3的定量形成，并同时将2还原回1。络合物2是可在室温下分离的氧锰(V)-类卟啉络合物的第一个例子。
The synthesis and characterization of an oxomanganese(V) corrolazine, (TBP)8(Cz)Mn(V)⋮O (2), are reported. This remarkably stable high-valent complex is obtained from the stoichiometric reaction of (TBP)8(Cz)Mn(III) (1) withm-CPBA and is easily purified by standard chromatographic methods on silica gel at room temperature. Complex2exhibits a diamagnetic1H NMR spectrum indicative of a low-spin d2Mn(V)⋮O species. LDI-TOFMS of2shows the predicted isotopic envelope atm/z1426.8. This envelope shifts to higher mass as expected after the facile exchange of the terminal oxo group with H218O. The resonance Raman spectrum of2either in solution or in the solid state shows a strongly enhanced Raman band for the stretching mode of the Mn−oxo bond, which also shifts as expected upon18O substitution:2(16O), 979 cm-1;2(18O), 938 cm-1(in CH2Cl2). Initial reactivity studies show that2rapidly transfers the terminal oxo ligand to PPh3, resulting in the quantitative formation of OPPh3and concomitant reduction of2back to1. Complex2is the first example of an oxomanganese(V)-porphyrinoid complex that can be isolated at room temperature.