Silyl-substituted Tetrylene Carbonyl Complexes

甲硅烷基取代的三萘嵌苯羰基配合物

• 批准号: 503665621
• 负责人: Professor Dr. Shigeyoshi Inoue
• 金额: --
• 依托单位: Institut für Siliciumchemie
• 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/503665621?language=en
• 关键词: Silyl; substituted; Tetrylene; Carbonyl; Complexes

Transition metal carbonyl complexes are common organometallic reagents and widely used as powerful catalysts in various chemical transformations. In search of environmentally benign and cost-efficient alternatives for transition metals, silicon and tin comprise great interest due to their high natural abundance and low-toxicity. Recently, we have succeeded in synthesis and isolation of silyl-substituted silicon carbonyl complexes (R2Si:⇄:CO) as stable compounds. In a very similar fashion to transition metals, the Si-CO bonding is achieved via sigma-donation of CO lone pair to an empty p orbital of the silylene and the strong C≡O bond is activated by the pi-backdonation, reinforced by bulky sigma-donating silyl groups on the Si center. The preliminary reactivity of silicon carbonyl complexes resembles that of transition metal carbonyls. The main objectives of this project are further reactivity investigations of silicon carbonyl complexes and development and reactivity studies of Ge and Sn analogues. The work programme contains two main parts. WP-1 describes the synthetic routes and preliminary results toward development of the heavier Group 14 carbonyl analogues R2E:⇄:CO (E = Ge, Sn). WP-2 consists of detailed description of the reactivity studies and strategies for development of catalytic transformations mediated by the silyl-substituted tetrylene carbonyl complexes R2E:⇄:CO (E = Si, Ge, Sn). Development of low-valent group 14 element carbonyl complexes will provide greater insights into the fundamental chemical properties of these species, which may emerge as ecologically friendly and cost-effective surrogates for industrially used catalysts.

过渡金属羰基复合物是常见的有机试剂，在各种化学转化中广泛用作强大的催化剂。为了寻找过渡金属的环境良性和成本效益的替代品，硅和锡由于它们的自然丰度高和低毒而引起了极大的兴趣。最近，我们在稳定的化合物中成功地成功地合成和分离了甲硅烷基取代的硅羰基复合物（R2SI：⇄：CO）。以与过渡金属非常相似的方式，Si-Co键合是通过将Co Lone Pair的Sigma延伸到sillyene的空孔的sigma键合，并且强烈的c程键被pi-backdonation激活，并被宽敞的si-backdonation通过Bulky Sigma-donony dononation in of。硅羰基复合物的初步反应性类似于过渡金属羰基。该项目的主要目标是对硅单复合物以及GE和SN类似物的发展和反应性研究的进一步反应性研究。工作计划包含两个主要部分。 WP-1描述了较重的组14羰基类似物R2E的综合途径和初步结果：⇄：CO（E = GE，SN）。 WP-2包括详细描述由由甲硅烷基取代的四烯羰基复合物r2e介导的催化转化的策略：⇄：co（e = si，ge，sn）。低价值组14组元素羰基复合物的开发将为这些物种的基本化学特性提供更​​多的见解，这些化学特性可能是对工业使用的催化剂的生态友好且具有成本效益的替代物。