Synthesis of electron-rich metal-substituted silylenes and their potential in small molecule bond activation

富电子金属取代硅烯的合成及其在小分子键活化中的潜力

• 批准号: 454766270
• 负责人: Professor Dr. Stephan Schulz
• 金额: --
• 依托单位: Anorganische Chemie - AK Schulz
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/454766270?language=en
• 关键词: Synthesis; electron; rich; metal; substituted

Acyclic silylenes are typically more reactive compared to their cyclic congeners due to their reduced singlet-triplet energy barrier and their promising potential for small molecule activation reactions, i.e. H2, CO or CO2, has been demonstrated in recent years. Even though these studies showed some parallels to the well-known chemistry of transition metal complexes, one of the most central reaction, the formation of metal carbonyl complexes by reaction with CO, is unknown for silylenes. We recently succeeded in the synthesis of the first room temperature-stabile silylene carbonyl complex [L1(Br)Ga]2Si–CO 6 by reaction of the metal substituted silylene [L1(Br)Ga]2Si: with CO. In this research project, we will try to generalize the synthesis of metal-substituted silylenes [L(X)M]2Si: and study the influence of the group 13 diyles LM as well as the starting silicon reagents SiX4 (X = Cl, Br, I, NR2, OR) on the reaction pathway as well as the stability of the resulting silylenes. We will furthermore investigate the potential of the silylene [L1(Br)Ga]2Si: and the carbonyl complex [L1(Br)Ga]2Si–CO 6 as well as of compound 5 in small molecule activation reactions with H2, CO, CO2, olefines C2R4, alkines C2R2, CN multiple bonds and E-H main group element hydrides. In situ NMR spectroscopic studies and computational calculations should provide a mechanistical understanding of the reaction and a detailed understanding of the electronic nature of the resulting complexes.

由于其单重态-三重态能垒的降低以及其在小分子活化反应（如H2， CO或CO2）中的潜力，近年来已被证明，无环硅烯通常比其环同系物更具活性。尽管这些研究显示了与众所周知的过渡金属配合物的一些相似之处，但最核心的反应之一，即与CO反应形成金属羰基配合物，对于硅烯来说是未知的。我们最近成功地合成了第一个房间temperature-stabile silylene羰基复杂(L1 (Br) Ga) 2 si-co 6的反应金属取代silylene (L1 (Br) Ga) 2 si:与有限公司在本研究项目中,我们将努力推广的合成metal-substituted silylenes (L (X) M) 2 si:研究集团13 diyles LM的影响以及从硅试剂SiX4 (X = Cl, Br,我、NR2或)在反应途径以及由此产生的silylenes的稳定性。我们将进一步研究硅烯[L1(Br)Ga]2Si：和羰基配合物[L1(Br)Ga]2Si - CO 6以及化合物5在与H2、CO、CO2、烯烃C2R4、烷烃C2R2、CN多键和E-H主基团元素氢化物的小分子活化反应中的潜力。现场核磁共振波谱研究和计算计算应该提供对反应的机械理解和对所得到的配合物的电子性质的详细理解。