Application of Imidazole-2-thione Substituents in Low-Coordinate Phosphorus Chemistry - Probing the Scope

作者：Majhi Paresh Kumar; Koner Abhishek; Schnakenburg Gregor; Kelemen Zsolt; Nyulaszi Laszlo^*; Streubel Rainer^*

来源：European Journal of Inorganic Chemistry, 2016, 2016(22): 3559-3573.

DOI：10.1002/ejic.201600703

• Phosphanes
• Nitrogen heterocycles
• Thiones
• N-heterocyclic carbenes
• Density functional calculations

A variety of (2-thioxoimidazol-4-yl) phosphanes have been synthesized with the prospect of further functionalization. Following a standard reaction protocol, P-amino (2a,b), P-chloro (3a,b), and P-hydrogeno (8a) phosphane derivatives were synthesized. Treatment of chlorophosphanes 3a,b with Lewis acids in dichloromethane/diethyl ether did not afford the expected phosphenium cation, instead ethoxyphosphane derivatives 5a,b were isolated. Treatment of secondary phosphane 8a with potassium hexamethyldisilazide afforded 2-thioxoimidazol-4-yl-substituted phosphanide derivative 10a, which was used to access dinuclear phosphanido borane 11a and tungsten complexes 12a. Furthermore, the first strong NMR evidence for P-anionic bis(imidazole-2-ylidene) 13a is provided. The first attempts to synthesize an (2-thioxoimidazol-4-yl)-substituted phosphanyl radical or its dimer, the tetrakis(2-thioxoimidazol-4yl)-substituted diphosphane, led exclusively to tris(2-thioxoimidazole-4-yl) phosphane 14a. These compounds were fully characterized spectroscopically and the structures of 2a, 3a, 7b, 8a, 10a, 11a, and 14a were determined by single-crystal X-ray crystallography. The challenges associated with the synthesis of some of the titled compounds were studied computationally.

• 出版日期2016-8