Intramolecularly group 15 stabilized aryltellurenyl halides and triflates
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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 = ½ (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) was reported (Ace = acenaphthyl). The synthesis of 7-15 was either achieved by salt metathesis reaction of 5-i-Pr2P-Ace-6-Li with TeCl2∙TMTU (8), TeBr2∙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 (13-15). 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 are 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-Cl 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).
Do , T G , Hupf , E , Nordheider , A , Lork , E , Slawin , A M Z , Makarov , S G , Ketkov , S Y , Mebs , S , Woollins , J D & Beckman , J 2015 , ' Intramolecularly group 15 stabilized aryltellurenyl halides and triflates ' Organometallics , vol. 34 , no. 21 , pp. 5341–5360 . DOI: 10.1021/acs.organomet.5b00813
Copyright © 2015 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/acs.organomet.5b00813
DescriptionThe Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged for financial support. The energy decomposition and deformation electron density analyses were carried out within the framework of the Project 14-13-00832 supported by the Russian Science Foundation.
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