Intramolecularly Group 15 Stabilized Aryltellurenyl Halides and Triflates

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• 作者：Truong Giang Do ; Emanuel Hupf ; Andreas Nordheider ; Enno Lork ; Alexandra M. Z. Slawin ; Sergey G. Makarov ; Sergey Yu. Ketkov ; Stefan Mebs ; J. Derek Woollins ; Jens Beckmann
• 刊名：Organometallics
• 出版年：2015
• 出版时间：November 9, 2015
• 年：2015
• 卷：34
• 期：21
• 页码：5341-5360
• 全文大小：992K
• ISSN：1520-6041

文摘

The preparation of a series of functionalized peri-substituted acenaphthyl compounds 6-Ph₂E-Ace-5-Br (1, E = As; 2, E = Sb), 6-Ph₂As-Ace-5-TeMes (3), 5-I-Ace-6-TeMes (4), 6-Ph₂Sb-Ace-5-TeMes (5), (6-Ph₂P-Ace-5)₂Te (6), [6-R₂E-Ace-5-Te]X (7, E = P, R = Ph, X = Cl; 8, E = P, R = i-Pr, X = Cl; 9, E = P, R = i-Pr, X = Br; 10, E = P, R = i-Pr, X = I; 11, E = P, R = i-Pr, X = 1/2 (TeI₆); 12, E = P, R = i-Pr, X = I₃; 13, E = P, R = Ph, X = O₃SCF₃; 14, E = As, R = Ph, X = O₃SCF₃; 15, E = Sb, R = Ph, X = O₃SCF₃), and [6-PhSb-Ace-5-TeMes]O₃SCF₃ (16) is reported (Ace = acenaphthyl). The synthesis of 7鈥?b>15 was achieved either by a salt metathesis reaction of 5-i-Pr₂P-Ace-6-Li with TeCl₂路TMTU (8), TeBr₂路TMTU (9), and TeI₄ (10 + 11) or by the aryl cleavage reaction of 6-R₂E-Ace-5-TeMes (E = P, As, Sb; R = Ph, i-Pr) with HgCl₂ (7), I₂ (12), and HO₃SCF₃ (13鈥?b>15). The reaction of 5 with triflic acid gave also rise to the formation of [6-PhSb-Ace-5-TeMes]O₃SCF₃ (16). All compounds have been characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. Complementary DFT studies including relaxed potential energy scans (PES) and subsequent topological analysis of the resulting electron and pair densities according to the AIM and ELI-D partitioning schemes were performed for the aryltellurenyl chlorides [6-Ph₂P-Ace-5-Te]Cl, [8-Me₂N-Nap-1-Te]Cl, and [8-Me₂P-Nap-1-Te]Cl in the gas phase and in MeCN solution, whereby the Te鈥揅l distances were systematically varied. The same analyses were carried out for the fully optimized [6-R₂E-Ace-5-Te]⁺ cations (E = P, As, Sb) and compared to those of the previously studied intermolecularly stabilized [R₃ETeMes]⁺ cations (E = P, As, Sb).