Do 2-coordinate iodine(i) and silver(i) complexes form nucleophilic iodonium interactions (NIIs) in solution?

Abstract

The interaction of a [bis(pyridine)iodine(I)]+ cation with a [bis(pyridine)silver(I)]+ cation, in which an iodonium ion acts as nucleophile by transferring electron density to the silver(I) cation, is reinvestigated herein. No...

The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena

“…Wilcox and collaborators successfully used LMA force constants to study weak interactions of 2-coordinate iodine(I) silver(I) with nucleophilic iodonium in solution. 204 Klufers et al recently reported the first Ru-complex, the dinitrosylruthenium [Ru-(NO) 2 (PPh 3 ) 2 , which can serve as a unique synchronous photoswitching device via a transformation of the double-linear to a double-bent Ru(NO) 2 core under nitrosyl charge conservation. 205 They used LMA to clarify that this trans-formation in not a [2 × 2] electron redox process, i.e., the observed redshift of the N−O stretching frequency occurs despite the lack of an additional electron-density transfer with both, the Ru−N and the N−O bonds becoming weaker upon bending.…”

“…They also recently applied LMA in a study on the rare cleavage of an aromatic C–C bond in ferrocene by insertion of an iridium nitrido nitrogen atom. Wilcox and collaborators successfully used LMA force constants to study weak interactions of 2-coordinate iodine­(I) silver­(I) with nucleophilic iodonium in solution . Klüfers et al recently reported the first Ru-complex, the dinitrosylruthenium [Ru­(NO) 2 (PPh 3 ) 2 , which can serve as a unique synchronous photoswitching device via a transformation of the double-linear to a double-bent Ru­(NO) 2 core under nitrosyl charge conservation .…”

Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds

“…58,59 The largest variation was observed for the asymmetric (Figure 3 (0.108 Å) a viable strategy toward instigating asymmetry in 3c-4e halogen-bonded complexes (whether neutral or positively/ negatively charged), and apparently one that can quantitatively rival the methodology of utilizing heteroleptic pairs of nucleophiles which suffers from disadvantages like ligand scrambling. 38,44 The N−I−N angles (Table 1) are predominantly symmetryrestrained and therefore perfectly linear (180°), with only minor deviations from linearity observed for the asymmetric complexes (maximum of 174. 8) Å (asymmetric) for all complexes (Table 1), which is at most 0.049 Å for the asymmetric complex L6H[3−I−3].…”

“…Erdélyi − has demonstrated with very precise and comprehensive studies in solution, supplemented with computational calculations, that the [N–I–N] + halogen bond has a very strong interaction ratio R XB < 0.65 ( R XB defined as the sum of the vdW radii of the interacting atoms divided by their contact distance), as well as being linear and symmetric with the iodine atom located in the center between the N atoms with a very small N–I distance variation. Over the last 5 years the field of halogen­(I) chemistry has expanded greatly, with recent developments including the first iodine­(I)-based capsules, − helicates, asymmetric complexes, , halogen-bonded organic frameworks (XOF), halogen-bonded hierarchical materials, and solid-state nucleophilic I + ···Ag + interactions. − …”

“…There are only two reported unrestrained asymmetric [N–I–N] + solid-state structures, both by the authors, , which possess heteroleptic ligands: [I­(pyridine)­(DMAP)]­PF 6 and [I­(mtz)­(DMAP)]­PF 6 (DMAP = 4-dimethylaminopyridine; mtz = 1-methyl-1,2,3-triazole). These complexes exhibited N–I bond length differences of 0.020 and 0.148/0.177 Å (as two independent molecules were present in the asymmetric unit cell), respectively, which makes the N–I bond length difference induced by hydrogen bonding in L8 H­[ 3 –I– 3 ] (0.108 Å) a viable strategy toward instigating asymmetry in 3c-4e halogen-bonded complexes (whether neutral or positively/negatively charged), and apparently one that can quantitatively rival the methodology of utilizing heteroleptic pairs of nucleophiles which suffers from disadvantages like ligand scrambling. , …”