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A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis,Structure, and Reactivity 下载免费PDF全文
Jingzhen Du Linbo Wang Prof. Dr. Meihua Xie Prof. Dr. Liang Deng 《Angewandte Chemie (International ed. in English)》2015,54(43):12640-12644
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C? Co? N core and a short Co? N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co? N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E? H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
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Erli Lu Oliver J. Cooper Jonathan McMaster Floriana Tuna Eric J. L. McInnes William Lewis Alexander J. Blake Stephen T. Liddle 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(26):6814-6818
We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)2] ( 5 , BIPMTMS=C(PPh2NSiMe3)2; Mes=2,4,6‐Me3C6H2; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse trans‐influence. Complex 5 reacts with tert‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)2(DMAP)2] ( 6 ). 相似文献
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Yuhei Katsuma Linlin Wu Zhenyang Lin Seiji Akiyama Makoto Yamashita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(1):323-327
The diboration of the C≡N bond in organic nitriles, and the N=N bond in azobenzene and pyridazine, by the highly Lewis‐acidic tetra(o‐tolyl)diborane(4) are reported. In the reactions with nitriles, azobenzene, and pyridazine, the addition of diborane(4) to the C≡N and N=N bonds was observed. Conversely, the N=N bond in phthalazine was cleaved by an addition/rearomatization sequence. 相似文献
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