Intramolecularly Group 15 Stabilized Aryltellurenyl Halides and Triflates

Abstract

The preparation of a series of functionalized peri -substituted acenaphthyl compounds 6-Ph 2 E-Ace-5-Br ( 1, E = As; 2, E = Sb), 6-Ph 2 As-Ace-5-TeMes ( 3 ), 5-I-Ace-6-TeMes ( 4 ), 6-Ph 2 Sb-Ace-5-TeMes ( 5 ), (6-Ph 2 P-Ace-5) 2 Te ( 6 ), [6-R 2 E-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 (TeI 6 ); 12, E = P, R = i -Pr, X = I 3; 13, E = P, R = Ph, X = O 3 SCF 3; 14, E = As, R = Ph, X = O 3 SCF 3; 15, E = Sb, R = Ph, X = O 3 SCF 3 ), and [6-PhSb-Ace-5-TeMes]O 3 SCF 3 ( 16 ) is reported (Ace = acenaphthyl). The synthesis of 7 – 15 was achieved either by a salt metathesis reaction of 5- i -Pr 2 P-Ace-6-Li with TeCl 2 ·TMTU ( 8 ), TeBr 2 ·TMTU ( 9 ), and TeI 4 ( 10 + 11 ) or by the aryl cleavage reaction of 6-R 2 E-Ace-5-TeMes (E = P, As, Sb; R = Ph, i -Pr) with HgCl 2 ( 7 ), I 2 ( 12 ), and HO 3 SCF 3 ( 13 – 15 ). The reaction of 5 with triflic acid gave also rise to the formation of [6-PhSb-Ace-5-TeMes]O 3 SCF 3 ( 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-Ph 2 P-Ace-5-Te]Cl, [8-Me 2 N-Nap-1-Te]Cl, and [8-Me 2 P-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-R 2 E-Ace-5-Te] + cations (E = P, As, Sb) and compared to those of the previously studied intermolecularly stabilized [R 3 ETeMes] + cations (E = P, As, Sb).