4.8 Article

The oxidation state in low-valent beryllium and magnesium compounds

期刊

CHEMICAL SCIENCE
卷 13, 期 22, 页码 6583-6591

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc01401g

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资金

  1. ERC StG [EU805113]
  2. Generalitat de Catalunya [2018 FI_B 01120]
  3. Fons Social Europeu [2018 FI_B 01120]
  4. Ministerio de Ciencia, Innovacion y Universidades (MCIU) [PGC2018-098212 B-C22]
  5. Ramon y Cajal program [RYC-2016-20489]
  6. FPU grant
  7. MCIU project [PGC2018-094644 B-C21]
  8. Department of Atomic Energy, Government of India [RTI 4007]
  9. CSIR, India [01(2863)/16/EMR-II]
  10. SERB, India [CRG/2019/003415]

向作者/读者索取更多资源

This article discusses the electronic structure of Lewis base-stabilized Be and Mg compounds and provides an explanation for their proposed oxidation states. The experimentally accomplished compounds rely on increasing the π-acidity of the ligand to strengthen the chemical bonds, and it is suggested that avoiding this interaction could lead to the presence of low-oxidation states.
Low-valent group 2 (E = Be and Mg) stabilized compounds have been long synthetically pursued. Here we discuss the electronic structure of a series of Lewis base-stabilized Be and Mg compounds. Despite the accepted zero(0) oxidation state nature of the group 2 elements of some recent experimentally accomplished species, the analysis of multireference wavefunctions provides compelling evidence for a strong diradical character with an oxidation state of +2. Thus, we elaborate on the distinction between a description as a donor-acceptor interaction L(0) ⇆ E(0) reversible arrow L(0) and the internally oxidized situation, better interpreted as a diradical L(-1) -> E(+2) <- L(-1) species. The experimentally accomplished examples rely on the strengthened bonds by increasing the pi-acidity of the ligand; avoiding this interaction could lead to an unprecedented low-oxidation state.

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