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.

与周期性同类物相比，无环晶烯具有更高的反应性，这是由于它们的单线 - 三曲线能量屏障的降低以及其对小分子激活反应的潜力，即H2，CO或CO2，近年来已经证明了H2，CO或CO2。尽管这些研究表明了众所周知的过渡金属复合物的相似之处，这是最中心的反应之一，但通过与CO反应的金属羰基复合物形成，是甲硅烷基烯烯是未知的。最近，我们通过金属取代的甲硅烷基[l1（br）ga] 2si：与CO。在此研究项目中，我们将试图概括地构成金属固定的silylenes [L（l1（br）ga ga] 2si：co。我们将试图概括地构成silylenes的合成，从而综合了13 i的xi，我们将试图概括地综合研究，我们最近成功地综合了第一个室温stabile silylene carbonyl carbonyl复合物[l1（br）ga ga] 2si-co 6。 LM以及反应途径上的simicon试剂six4（x = cl，br，i，nr2，或）以及所得的甲硅烷基烯的稳定性。我们还将研究甲硅烷基[L1（BR）GA] 2SI的潜力：和羰基复合物[L1（BR）GA] 2SI-CO 6以及与H2，CO，CO，CO2，CO2，Olefines C2R4的小分子激活中的化合物5中的化合物5中的化合物5中的化合物C2R4，碱C2R2，C2R2，C2R2，Cn Mutternoter Boldy element和E-H Main Hydrides。原位NMR光谱研究和计算计算应提供对反应的机械理解，并详细了解所得复合物的电子性质。