LAUSR

Arenes [C6H3R(TMS)(OTf); also called benzyne/aryne precursors] containing inter‐related leaving groups Me3Si (TMS) and CF3SO3(OTf) on the adjacent positions (1,2‐position) are generally converted to their corresponding aryne‐intermediates via the addition of fluoride anion (F−) and subsequent elimination of TMS and OTf groups. This reaction is believed to proceed via the formation of an anionic intermediate [C6H4(TMS‐F)(OTf)]−. The EDA‐NOCV analysis (EDA‐NOCV = energy decomposition analysis‐natural orbital for chemical valence) of over 35 such precursors of varied types have been reported to reveal bonding and stability of CArSi and COTf bonds. EDA‐NOCV showed that the nature of the CArSi bond of C6H3R(TMS)(OTf) can be expressed as both dative and electron sharing [CArSi, CAr→Si]. The CArOTf bond, on the other hand, can be described explicitly as dative [CAr←OTf]. The nature of CArSi bond of [C6H4(TMS‐F)(OTf)]− exclusively changes to covalent dative σ‐bond CAr→S(Me)3F on the attachment of F− to the TMS group of C6H4(TMS)(OTf). Introduction of σ‐electron withdrawing group (like OMe, NMe2, and NO2) to the ortho‐position of the TMS group of functionalized arynes C6H3R(TMS)(OTf) prefer to have a covalent dative σ‐bond (CAr→Si) over an electron‐sharing covalent σ‐bond (CArSi). If this σ‐electron withdrawing group is shifted from ortho‐position to meta‐ and para‐positions, then the preference for a dative bond decreases significantly, implying that the electronic effect on the nature of chemical bonds affects through bond paths. This effect dies with distance, similar to the well‐known inductive effect.