Molybdenum Complexes Supported by Mixed NHC/Phosphine Ligands: Activation of N2 and Reaction With P(OMe)3 to the First Meta-Phosphite Complex
Molybdenum Complexes Supported by Mixed NHC/Phosphine Ligands: Activation of N2 and Reaction With P(OMe)3 to the First Meta-Phosphite Complex
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DOI：
10.1002/chem.201405737
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发表时间：
2015-01-12
影响因子：
4.3
通讯作者：
Tuczek, Felix
中科院分区：
文献类型：
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作者：
Gradert, Christian;Stucke, Nadja;Tuczek, Felix
钼(0)二氮配合物在混合NHC/phosphine钳形配体PCP的支持下，由于金属中心具有非常富电子的金属，表现出对N-2配体的极端活化。用亚磷酸盐代替膦作为配体可以提高这些化合物的低热稳定性。在亚磷酸三甲酯和N-2的存在下，通过汞齐还原[MoCl3(PCP)]，得到了高活性、室温稳定的二氮配合物[Mo(N-2)(PCP)(P(OMe)(3))(2)]。作为第二产物，含有间亚磷酸酯配体P(O)（OMe）的第一个过渡金属配合物就是由这个反应产生的。
Molybdenum(0) dinitrogen complexes, supported by the mixed NHC/phosphine pincer ligand PCP, exhibit an extreme activation of the N-2 ligand due to a very -electron-rich metal center. The low thermal stability of these compounds can be increased using phosphites instead of phosphines as coligands. Through an amalgam reduction of [MoCl3(PCP)] in the presence of trimethyl phosphite and N-2 the highly activated and room-temperature stable dinitrogen complex [Mo(N-2)(PCP)(P(OMe)(3))(2)] is obtained. As a second product, the first transition metal complex containing the meta-phosphite ligand P(O)(OMe) originates from this reaction.