Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me 3 CNCN) − , that bind potassium both end-on and side-on in the same single crystal
Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me 3 CNCN) − , that bind potassium both end-on and side-on in the same single crystal
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N , N α-二叔丁基碳二亚胺的还原裂解生成叔丁基氰酰胺配体 (Me 3 CNCN) α ，该配体在同一单晶中以端接和侧接方式结合钾
DOI：
10.1107/s205698902000732x
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Evans, William J.
中科院分区：
文献类型：
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作者：
Chung, Amanda B.;Ziller, Joseph W.;Evans, William J.
N，N′-二叔丁基碳二亚胺，Me 3CN =C= NCMe 3，在GdII配合物[K（18-crown-6）2][GdII（NR 2）3]（R = SiMe 3）存在下发生还原裂解，形成一种新型配体，叔丁基氰胺阴离子，（Me 3CNCN）−。这种新的配体可以用一个或两个供体原子结合金属，这一点可以通过分离出一个含有末端和侧面结合的叔丁基氰胺阴离子（Me 3CNCN）−的钾盐的单晶来证明。该晶体含有[K（18-crown-6）（H2O）][NCNCMe 3-kN]，其中一个（tBuNCN）−阴离子与18-crown-6和水连接的钾端对配位，以及[K（18-crown-6）][η2-NCNCMe 3]，其中18-crown-6钾侧对配位到末端N-C键。该单晶还含有1当量的1，3-二叔丁基脲，（C9 H20 N2 O），它参与氢键，可以稳定整个组装，即水（叔丁基氰氨基）（1，4，7，10，13，16-六氧杂环十八烷）钾（I）-（叔丁基氰氨基）（1，4，7，10，13，16-六氧杂环十八烷）钾（I）-N，N′-二叔丁基碳二亚胺（1/1/1）[K（C5 H9 N2）（C12 H24 O 6）]·[K（C5 H9 N2）（C12 H24 O 6）（H2O）]·C9 H20 N2。
N,N′-Di-tert-butylcarbodiimide, Me3CN=C=NCMe3, undergoes reductive cleavage in the presence of the GdII complex, [K(18-crown-6)2][GdII(NR2)3] (R = SiMe3), to form a new type of ligand, the tert-butylcyanamide anion, (Me3CNCN)−. This new ligand can bind metals with one or two donor atoms as demonstrated by the isolation of a single crystal containing potassium salts of both end-on and side-on bound tert-butylcyanamide anions, (Me3CNCN)−. The crystal contains [K(18-crown-6)(H2O)][NCNCMe3-kN], in which one (tBuNCN)− anion is coordinated end-on to potassium ligated by 18-crown-6 and water, as well as [K(18-crown-6)][η2-NCNCMe3], in which an 18-crown-6 potassium is coordinated side-on to the terminal N—C linkage. This single crystal also contains one equivalent of 1,3-di-tert-butyl urea, (C9H20N2O), which is involved in hydrogen bonding that may stabilize the whole assembly, namely, aqua(tert-butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–(tert-butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–N,N′-di-tert-butylcarbodiimide (1/1/1) [K(C5H9N2)(C12H24O6)]·[K(C5H9N2)(C12H24O6)(H2O)]·C9H20N2.