Structural studies on diaryl selenide dihalides in solution: molecular complex formation of substituted diphenyl selenides with bromine

How do weak Z–X–X and stronger X–Z–X interactions affect NMR chemical shifts of chalcogenide dihalides, R2Z·X2? Theoretical background on the structural prediction of R2Z·X2 through chemical shifts in solutions

“…To show the outline of discussion, some selenides (1, 3 [6], 5, 7, 9-13 [20], 14-15 [11,20], and16 [20]) and sulfides (2, 4, 6, and 8) examined so far are shown in Chart 1 [11,15,[18][19][20]. Table 1 ZX2 , respectively).…”

“…Diphenyl selenides (7) itself form TBP with bromine in solutions as shown in Chart 2 [11,15,[18][19][20]. How are the structures of bromine adducts of substituted diphenyl selenides with bromine determined?…”

“…Consequently, the bulkiness around Z will be more severe for TBP than that for MC. The increased bulkiness around Z prefers MC to TBP [18][19][20]. Namely, it is possible to prepare hypervalent chalcogen compounds other than those predicted from the general rule based on χ , by modulating electronic and/or steric conditions around chalcogens in organic chalcogen compounds.…”

“…The criteria were applied to predict the structures of various chalcogenide dihalides in solutions, and the high applicability was well established. Typical selenides and sulfides examined (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) are shown in Chart 1 [11,15,[18][19][20].…”

A Structural Comparison of Organoterminated Selenide, Diselenide, and Triselenide

“…The measurements were performed with a Bruker APEX-II CCD using graphitemonochromatized Mo K α radiation at 100 K on a yellow needle shaped crystal (0.23 × 0.10 × 0.08 mm): C 18 The structure was solved by direct methods (SHELXS-97) and refined by full-matrix least-square techniques against F 2 (SHELXL-97). 25 The nonhydrogen atoms were refined with anisotropic displacement parameters without any constraints.…”