Affiliation:
1. Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry and Materials Science Northwest University Xi'an 710069 P. R. China
2. Laboratory of Medicinal Molecule Science and Pharmaceutics Engineering Ministry of Industry and Information Technology School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing 100081 P. R. China
Abstract
AbstractThe α‐diimine‐ligated dimagnesium(I) compound [K(thf)3]2[LMg−MgL] (1, L=[(2,6‐iPr2C6H3)NC(Me)]22−) displays diverse reactivities toward carbodiimides (RN=C=NR) with different R substituents. In the reaction of 1 with Me3SiNCNSiMe3, one of the easily leaving trimethylsilyl groups is lost to yield the Me3SiNCN− moiety that either bridges two MgII centers (2) or terminally coordinated (3). In contrast, with the similarly bulky tBuNCNtBu, the carbodiimide inserts into Mg−Mg bond with accompanying C−H activation of a ligand or solvent (products 4 and 5). In the case of dicyclohexyl or diisopropyl carbodiimide, reductive C−C coupling of two RNCNR molecules occurs to form the [C2(NR)4]2− diamido moiety, which bridges two Mg centers, giving complexes [{K(dme)2}2LMg(μ‐{C2(NR)4})MgL] (6, R=Cy; 7, R=iPr) and [L⋅−Mg(μ‐{C2(NR)4})MgL⋅−] (8). Most interestingly, upon treating 1 with Me3SiC≡CSiMe3, the acetylide complex [K(dme)][LMg(C≡CSiMe3)(dme)] (9) was prepared, which undergoes a rare “double insertion” with CyNCNCy to afford [K(solv)][K(dme)2LMg(NCy)2C−C≡C−C(NCy)2MgL] (10) containing an acetylenediide‐coupled bis(amidinate) ligand that bridges two Mg atoms.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
2 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献