Transannular bonding

Figure 10 Annular k bonding, transannular k -k bonding (a) and additional charge delocalization through an np2 >na interaction (b)...

The homolysis of tertiary hypochlorites for the production of oxy radicals is well known." The ease with which secondary hypohalites decompose to ketones has hampered the application of hypohalites for transannular reactions. However the tendency for the base-catalyzed heterolytic decomposition decreases as one passes from hypochlorites to hypobromites tohypoidites. Therefore the suitability of hypohalites for functionalization at the angular positions in steroids should increase in the same order. Since hypoidites (or iodine) do not react readily with ketones or carbon-carbon double bonds under neutral conditions hypoiodite reactions are more generally applicable than hypochlorite or hypobromite decompositions. 

The bicyclic compound 8.17 also serves as a source of the five-membered ring 8.20 upon reduction with SbPhs. In contrast to the related S or Se systems, 8.11a and 8.11b, both Cl substituents are attached covalently to Te in 8.20. Reaction of 8.20 with an excess of AsFs in SO2 produces the eight-membered cyclic [Tc2S2N4] dication, which exhibits a Te-Te bond length of 2.88 A (cf. 2.70 A for a Te-Te single bond) and no transannular S S bonding J... 

The eight-membered rings 13.14 normally adopt boat conformations in the solid state with short S=N bond distances (1.51-1.52 A) that are typical of sulfur diimides. There are no transannular S S contacts. The sole exception is the antimony derivative BuSb(NSN)2Sb Bu, which is a planar eight-membered ring. 

Transannular Te N interactions have also been employed to stabilize compounds of the type 15.24 with terminal Te=E (E = S, Se) bonds.The Te=Se bond length in 15.24b is 2.44 A (cf. 2.54 A for a Te-S single bond) and d(Te N) = 2.62 A. Intramolecular coordination was also employed in the isolation of the first aryl-selenenium and -tellurenium cations 15.25a,b as [PEg] salts. 

The stmcture of the compound 67b was determined by X-ray (95JA6388). The length of the Te=Se bond (2.445 A) is 0.1 A shorter that in bis(2-ethylcarboxy-phenyltellurenyl) selenide (81CSC1353), which points to a greater double bond character of this bond in the former compound. Selenoxide 67b has a boat conformation. The length of the transannular Te- N bond (2.620 A) is appreciably shorter than the corresponding van der Waals contact (3.70 A). The intramolecular coordination Te- N bond thus formed contributes to the stabilization of the boat conformation of the compounds 67. 

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