01880nas a2200229   4500008004100000022001400041245009900055210006900154260000900223300001500232490000700247520113600254653001301390653001201403653002001415653001401435653002401449100001801473700002501491700001701516856011701533       2025                        eng d  a1439-423500aPushing the boundaries of pnictogen-bonding organocatalysis: a clash of Sb(III) versus Bi(III)0 aPushing the boundaries of pnictogenbonding organocatalysis a cla  cAUG   ae2025002650 v263 a<p>
	The sigma-hole-mediated noncovalent organocatalysis involving the pnictogen (Pn) elements has thus far been explored mostly from nitrogen to antimony, with antimony identified as the most effective catalyst. Herein, density functional theory calculations have been carried out to demonstrate that tri-aryl (Ar)-substituted bismuth(III) complexes can outperform their antimony counterparts in both anion (Cl-) binding and catalytic activity. Using a range of computational methods, a good correlation between the sigma-hole strength, chloride binding affinity, and the reaction barrier is established. Notably, the findings reveal that dispersion interactions are the dominant force in catalysts with weaker sigma-holes, while electrostatic interactions prevail in catalysts with stronger sigma-holes (for the anion abstraction step). In all cases, Bi(III) catalysts emerge as the winner over the Sb(III) analogues. Additionally, beyond the primary Pn. . .Cl interactions, several secondary interactions such as Cl. . .H/F-C(Ar) and Cl-. . . H-C(Si-TBS) also play a significant role in stabilizing the transition states.</p>
10aAntimony10aBismuth10aorganocatalysis10apnictogen10asigma (sigma) holes1 aSharma, Jyoti1 aDash, Soumya, Ranjan1 aVanka, Kumar  uhttps://library.ncl.res.in/content/pushing-boundaries-pnictogen-bonding-organocatalysis-clash-sbiii-versus-biiii