Direct fluorination of dimethyl bicyclo[1.1.1]pentane-1,3-dicarboxylate, obtained from [1.1.1]propellane prepared by an improved synthetic procedure, furnished esters of 14 of the 15 possible bridge-fluorinated bicyclo[1.1.1]pentane-1,3-dicarboxylic acids, isolated by preparative GC. Calculated geometries reflect the substitution pattern in a regular fashion compatible with Bent's rules. Considerable additional strain is introduced into the bicyclo[1.1.1]pentane cage by polyfluorination; it is calculated to be as high as 33-35 kcal/mol for hexasubstitution. Three arrangements of the fluorine substituents are especially strain-rich: geminal, proximate, and W-related. The (1)H, (13)C, and (19)F NMR spectra exhibit a striking variety of chemical shifts and long-range coupling constants. These are in good agreement with results calculated with neglect of the bridgehead substituents for all of the chemical shifts by the GIAO-RHF/6-31G//RHF/6-31G and GIAO-RHF/6-31G//MP2/6-31G methods and for many of the coupling constants by the EOM-CCSD/6-311G//MP2/6-311G method. The proximate (4)J(FF) constants are particularly large (50-100 Hz) and show an inverse linear dependence on the calculated F-F distance in the range 2.43-2.58 A.

A series of 3-halo-substituted bicyclo[1.1.1]pentane-1-carboxylic acids 1 (Y = COOH; X = F, Cl, Br, I, and CF(3)) as well as the parent compound 1 (Y = COOH, X = H) have been prepared, and a study of some of their properties have been made. It was found that their reactions with xenon difluoride cover a wide range of reactivities. On one hand, the fluoro acid 1 (Y = COOH, X = F) displayed no apparent reaction at all while, on the other, the bromo acid 1 (Y = COOH, X = Br) and parent compound 1 (Y = COOH, X = H) underwent ready reaction with complete disintegration of the ring system. A possible explanation is advanced based on polar kinetic and thermodynamic effects governing the lifetime of an intermediate acyloxy radical species. The relative ease of oxidation of the carboxylates 1 (Y = COO(-); X = H, F, Cl, Br, I, CF(3), and COOCH(3)), as mirrored by their peak oxidation potential values (E(p)) determined by cyclic voltammetry, also covers a wide range. These data coupled with the dissociation constants (pK(a)) of some of the acids 1 (Y = COOH; X = H, F, Cl, and CF(3)) reflect significantly on the modes of transmission of electronic effects acting through the bicyclo[1.1.1]pentane ring system.