Mukherjee Debabrata, Shirase Satoru, Beckerle Klaus, Spaniol Thomas P, Mashima Kazushi, Okuda Jun
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Dalton Trans. 2017 Jul 4;46(26):8451-8457. doi: 10.1039/c7dt01727h.
Heteroleptic bis(silyl)amides of magnesium and calcium [(L)M{N(SiMe)}] [M = Mg, Ca; LH = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; (MeTACD)H] were previously synthesized from LH and [M{N(SiMe)}]. Strontium bis(silyl)amides [Sr{N(SiMe)}(thf)] and [Sr{N(SiHMe)}(thf)] reacted with LH to give different types of products, depending on the presence of the β-SiH function. While the former underwent protonolysis to give the amido-bridged dimer [(L)Sr{N(SiMe)}] (1), the latter gave the adduct [(LH)Sr{N(SiHMe)}] (2) as a stable solid. 2 slowly underwent an intramolecular Si-H/H-N dehydrocoupling in solution to give [{(L)SiMeN(SiHMe)}Sr{N(SiHMe)}] (3) by liberating H. The results of transamination of 1 with HN(SiHMe) depended on the relative stoichiometric ratio. A 1 : 1 mixture in n-pentane gave [{(L)SiMeN(SiHMe)}Sr{N(SiMe)}] (4) and H, while excess HN(SiHMe) gave the adduct 2 under similar conditions. Compounds 2 and 3 exhibit Sr↼H-Si interactions according to X-ray crystallography, NMR, and IR spectroscopy. Lighter congeners of elusive [(L)Sr{N(SiHMe)}] were isolable for Mg (5) and Ca (6).
镁和钙的杂配双（硅基）酰胺[（L）M{N(SiMe)}] [M = Mg，Ca；LH = 1,4,7-三甲基-1,4,7,10-四氮杂环十二烷；（MeTACD）H]先前是由LH和[M{N(SiMe)}]合成的。锶双（硅基）酰胺[Sr{N(SiMe)}(thf)]和[Sr{N(SiHMe)}(thf)]与LH反应生成不同类型的产物，这取决于β-SiH官能团的存在。前者发生质子解反应生成酰胺桥连二聚体[（L）Sr{N(SiMe)}]（1），而后者生成加合物[（LH）Sr{N(SiHMe)}]（2）作为稳定的固体。2在溶液中缓慢发生分子内Si-H/H-N脱氢偶联反应，通过释放H生成[{(L)SiMeN(SiHMe)}Sr{N(SiHMe)}]（3）。1与HN(SiHMe)转氨反应的结果取决于相对化学计量比。在正戊烷中1:1的混合物生成[{(L)SiMeN(SiHMe)}Sr{N(SiMe)}]（4）和H，而过量的HN(SiHMe)在类似条件下生成加合物2。根据X射线晶体学、核磁共振和红外光谱，化合物2和3表现出Sr↼H-Si相互作用。难以捉摸的[（L）Sr{N(SiHMe)}]的较轻同系物对于Mg（5）和Ca（6）是可分离的。
