Synthesis of Aminosilane Chemical Vapor Deposition Precursors and Polycarbosilazanes through Manganese-Catalyzed Si–N Dehydrocoupling
Synthesis of Aminosilane Chemical Vapor Deposition Precursors and Polycarbosilazanes through Manganese-Catalyzed Si–N Dehydrocoupling
复制标题
锰催化硅氮脱氢偶联合成氨基硅烷化学气相沉积前体和聚碳硅氮烷
DOI：
10.1021/acssuschemeng.2c00008
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发表时间：
2022
影响因子：
8.4
通讯作者：
Trovitch, Ryan J.
中科院分区：
文献类型：
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作者：
Nguyen, Thao T.;Mukhopadhyay, Tufan K.;MacMillan, Samantha N.;Janicke, Michael T.;Trovitch, Ryan J.
以Si-N键为特征的化合物对电子和涂层工业具有广泛的重要性。目前，氨基硅烷和聚硅氮烷是通过在卤代硅烷中加入胺来制备的，这是一种低效的方法，会产生化学计量的铵盐废物。在这里，我们描述了通过胺到硅烷(SiH4)的常温脱氢偶联，合成了氨基硅烷化学气相沉积前驱体、聚碳硅氮烷和全氢聚硅氮烷。具体地说，β-二酮基氢化锰二聚体[(2，6-iPr2PhBDI)Mn(μ-H)]2已被用于催化从仲胺和伯胺生成商业氨基硅烷单体，从二胺和三胺合成高度交联型聚碳硅氮烷粉末，以及从氨合成过氢聚硅氮烷。在[(2，6-iPr2PhBDI)Mn(μ-H)]2中加入异丙胺后，[(2，6-iPr2PhBDI)Mn(σ-H)]2发生了σ键的歧化反应，生成了[(2，6-iPr2PhBDI)Mn(μ-NHIPr)]2.在SiH4存在下，跨新形成的Mn-N键的H-Si加成使催化剂再生，为无卤化的Si-N键的形成提供了直接的催化循环.
Compounds that feature Si–N bonds are of widespread importance to the electronics and coating industries. Aminosilanes and polysilazanes are currently prepared by adding amines to halosilanes, an inefficient methodology that generates stoichiometric quantities of ammonium salt waste. Herein, we describe the syntheses of aminosilane chemical vapor deposition precursors, polycarbosilazanes, and perhydropolysilazane through the ambient-temperature dehydrocoupling of amines to silane (SiH4). Specifically, the β-diketiminate manganese hydride dimer [(2,6-iPr2PhBDI)Mn(μ-H)]2has been used to catalyze the formation of commercial aminosilane monomers from secondary and primary amines, highly cross-linked polycarbosilazane powders from diamines and triamines, and perhydropolysilazane from ammonia. The mechanism of dehydrocoupling was explored, and the addition of isopropylamine to [(2,6-iPr2PhBDI)Mn(μ-H)]2resulted in σ-bond metathesis to eliminate H2and generate [(2,6-iPr2PhBDI)Mn(μ-NHiPr)]2. In the presence of SiH4, H–Si addition across newly formed Mn–N bonds regenerates the precatalyst, offering a straightforward catalytic cycle for halogen-free Si–N bond formation.