Identification of key functionalization species in the Cp*Ir(iii)-catalyzed-ortho halogenation of benzamides

Abstract

Cp*Ir(iii) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source.

Carbonyl hypoiodites from pivalic and trimesic acid and their silver(i) intermediates

“…Compound 2c lies between the two literature examples with respect to O–I–N bond angles, but these angles are undoubtedly heavily influenced by other factors than the electronic contributions of the substituents, such as packing effects, making this a less informative metric to consider in comparison to the bond lengths. Comparisons could also be drawn with the literature complex [N n Bu 4 ][AcO–I–succinimide], 48 despite its anionic charge, given that it contains the same linear O–I–N motif. However, the I–O (2.293(2) and 2.299(2) Å) and I–N (2.166(2) and 2.168(2) Å) bond lengths of that complex clearly reflect that it contains significant covalent character in its I–N bond, 5 and is therefore best described as an acetate anion coordinating to a neutral molecule of N -iodosuccinimide.…”

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

“…81,82 The [N•••I•••O] − halogen-bond complex encompassing N-iodosuccinimide and acetate as Lewis bases has been crystallized and showed a linear geometry with d NI = 2.17 Å (R XB = 0.61) and d OI = 2.30 Å (R XB = 0.66). 101 81,82 The interaction energy was estimated to be up to 120 kJ/mol in CDCl 3 by measuring the association constants by NMR titrations (K a up to 10 8 M). Analogous bromine(I)-centered [N•••Br•••O] complexes have also been assessed and showed similar yet weaker bonds, a trend that fits that observed for the bis(pyridine) complexes of bromine(I) and iodine(I).…”

“…62,63 The (relative) stabilities of complexes formed upon the interaction of a halogenated Lewis base with a Journal of the American Chemical Society 6c. This reaction is most relevant for the estimation of the energies of the asymmetric halogen-bond complexes of, for instance, Nhalosaccharins, 50 N-halosuccinimides, 112 and hypoiodates 55,56 as well as of fluorine-centered halogen-bond complexes. 19 The energy cost of stretching a D−X covalent to a D ■ APPLICATIONS Halogen Transfer Reactions.…”

Halogen Bonding and/or Covalent Bond: Analogy of 3c–4e N···I···X (X = Cl, Br, I, and N) Interactions in Neutral, Cationic, and Anionic Complexes

“…, 1,4-diazabicyclo[2.2.2]-octane (DABCO) are characterized by the very short I···N bonds of about 2.25–2.30 Å, which are close to that in the cationic or anionic associations comprising N–I + –N fragments [ e.g. , bis­(1,4-diazabicyclo[2.2.2]­octane)­iodine­(I), or 1,1′-iodanylbis­(pyrrolidine-2,5-dione)]. − Computational analysis also demonstrated that many characteristics of the bonding in complexes of DABCO with IX are close to those in the trihalide anions . Similar short N–I distances were also observed in the complexes of some nucleophiles with N -iodosaccharin and N -iodosuccinimide. − As such, several previous publications suggested that the interaction in the strong HaB complexes ( e.g.…”