Cobalt Cyclopentadienyl-Phosphine Dinitrogen Complexes |
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Authors: | Gao-Xiang Wang Xuechao Yan Jianhao Yin Zhu-Bao Yin Prof. Junnian Wei Prof. Dr. Zhenfeng Xi |
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Affiliation: | Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and, Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871 P. R. China |
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Abstract: | By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl2, the corresponding cobalt chlorides ( 1 , L CoIICl) were prepared. By reducing complexes 1 with KHBEt3 under a N2 atmosphere, bridging end-on complexes, L CoI−N2−CoI L ( 2 a and 2 b ), were successfully obtained. 15N2-labeled [15N2]- 2 a was prepared under 15N2/14N2 exchange in THF solution. L CoI−N2−CoI L complex 2 a could react with P4 molecules to release N2 and generate a Co−P4−Co moiety 4 . Further reduction of complex 2 b led to cleavage of a P−C bond in the cyclopentadienyl-phosphine ligand to provide novel μ-PCy2-bridged Co0−N2 complex 5 . DFT calculations confirmed the experimental observations. |
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Keywords: | cobalt dinitrogen activation dinitrogen fixation P4 activation |
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