Secondary Bonding as a Force Dictating Structure and Solid-State Aggregation of the Primary Nitrene Sources (Arylsulfonylimino)iodoarenes (ArINSO₂Ar‘)

Abstract

Iodonium ylides of the form ArINSO 2 Ar′ (Ar ) m-tolyl, Ar′ ) p-nitrophenyl (1); Ar ) m-tolyl, Ar′ ) phenyl (2); Ar ) m-tolyl, Ar′ ) p-tolyl (3); Ar, Ar′ ) p-tolyl (4)) have been prepared and crystallographically characterized. Comparisons to previously structurally characterized members of this class of materials (PhINTs (Ts ) p-toluenesulfonyl), o-TolylINTs, MesINTs) demonstrate that apparently minor perturbations of the aromatic rings have substantial consequences on the supramolecular assemblies of these materials. The structures range from zigzag polymers (PhINTs, MesINTs), linear polymers (o-TolylINTs), layered structures (1), two-dimensional ladders (2, 3, o-TolylINTs), to even three-dimensional stepladders (4). Ab initio calculations for a model molecule, PhINSO 2 -Ph, corroborate the presence of a I-N single bond and show considerable charges being localized on the I, N, S, and O atoms (+, -, +, andcharges, respectively). Extensive attractive networks of I‚‚‚O and I‚‚‚N secondary bonds thus dominate the solid-state polymers. Within the monomeric units of ArINSO 2 Ar′, a U-turn-shaped motif is observed. This structural shape appears to optimize secondary bonding contacts between charged INSO 2 arrays. The structures of ArINSO 2 Ar′ have been systematically characterized.

Development of Imino‐λ3‐iodanes with Improved Reactivity for Metal‐Free [2+2+1] Cycloaddition‐Type Reactions

“…Furthermore, the intermolecular I⋅⋅⋅N bond distance of 1 d (2.951 Å) is longer than those of PhINTs (2.482 Å) and the o ‐alkoxy analogue (2.735 Å) . A similar elongation of intermolecular I⋅⋅⋅N bond (3.020 Å) is observed for structure of 1 c (Figure ). This would be probably due to trans influences of aryl ligand along with distortion of C−I⋅⋅⋅N bond angles.…”

Imination of Sulfides and Sulfoxides with Sulfonylimino‐λ3‐Bromane under Mild, Metal‐Free Conditions

“…[4][5][6][7] In the absence of metal catalysts, the nitrenoid-transfer reaction of imino-l 3 -iodanes does not take place or requires harsh reaction conditions, [8] partly due to their insoluble nature in common organic media, evoked by the highly aggregated polymeric zigzag structure. [9] Recently, we reported the synthesis of Group 17 analogue trifluoromethanesulfonyliminoA C H T U N G T R E N N U N G (aryl)-l 3 -bromane (1). [10] The sulfonylimino-l 3 -bromane 1 functions as an electrophilic imido-group donor and directly undergoes stereospecific aziridination of olefins with retention of stereochemistry and transylidation to iodobenzenes and pyridines.…”

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

“…[20] This can lead to varied polymeric assemblies, which can be stabilized through secondary interactions with the oxygen atoms of the sulfonyl moiety. [21] Thus, iodinanes generally are poorly soluble and the catalytic reactions that employ them are heterogeneous and rather slow. This problem can be overcome by the preparation of iodinane B in which an additional sulfonyl group is put on the aryl group attached to the iodine center (Scheme 3).…”