Scientists of the Zelinsky Institute studied the reaction of diphenyl disulfide with Lappert's germylene
The use of transition metals catalysis provoked the rapid development of organic chemistry in the second half of the 20th century and continues to play a key role in the development of modern organic synthesis. Platinum group metals are actively used as catalysts. However, their extraction is carried out only in a small number of locations, and their derivatives are not only expensive, but also quite toxic. In recent decades, more accessible and safe low-valent derivatives of elements of the main groups of the Periodic system, such as aluminum, silicon, and germanium, have been actively considered as a candidates for the role of highly efficient catalysts. The simultaneous presence of an unshared electron pair and a vacant orbital on the same reaction center brings them closer to transition metals. The main problem hindering their practical use is their instability, which requires additional stabilization of their derivatives.
Researchers at the Laboratory for the Chemistry of Carbenes and Other Unstable Molecules of the ZIOC are actively involved in the chemistry of organogermanium compounds. In one of their latest works, using the example of the reaction of diphenyl disulfide with Lappert's germylene, one of the first obtained stable low-valent derivatives of the main group elements, they showed that the presence of donor N-, O-, P- and S-ligands not only thermodynamically stabilizes the reaction center of a low-valent element of main group, but also increases the rate of the oxidative addition step. This may be due to an increase in the level of the highest occupied germylene molecular orbital under the influence of the donor ligand. From a practical point of view, this discovery can be useful in creating promising catalysts based on low-valent derivatives of the main group elements by varying the structure of ligands and fine-tuning their redox properties, for example, by replacing donor and acceptor substituents.
Pavel G. Shangin, Anna Ya. Akyeva, Daria M. Vakhrusheva, Mikhail E. Minyaev, Badma N. Mankaev, Victoriya A. Balycheva, Andrey V. Lalov, Mikhail P. Egorov, Sergey S. Karlov, Mikhail A. Syroeshkin The Role of Ligands in Oxidative Addition Chemistry of Low-Valent Main Group Derivatives: Not Only Stabilization but Also Activation // Organometallics 2023, accepted manuscript. DOI: 10.1021/acs.organomet.2c00607.