A 2,2′-bipyridine coordination complex of [ICl<sub>2</sub>]<sup>+</sup>

Shaw, Andrew J. M.; Corbo, Robert; Wilson, David J.; Dutton, Jason L.

doi:10.1039/c4dt03549f

Cited by 7 publications

(5 citation statements)

References 36 publications

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“…The pyridine is located opposite the phenyl ring resulting in a square planar iodine geometry. The N-I distance is 2.750(4) Å which is indicative of the presence of a much stronger type halogen bond than in 1 (RNI = 0.78, =0.98), 12, 13 but significant longer than those present in Weiss' reagent (2.22 Å) , 14,15 bipyridine adduct of [ICl2] + (2.27 Å ), 16 or the 4-coordinate pyridine adduct of iodine triacetate (2.406 Å). 17 NMR titration experiments followed by fitting using BindFit 18,19 with 1, 2, 3, 4, 5 and 10 equivalents of pyridine relative to PhICl2 in CDCl3 gave a binding constant of 0.7 M -1 and binding behavior consistent with a host-guest or coordinative interaction, rather than displacement.…”

Section: Resultsmentioning

confidence: 98%

On the Activation of PhICl2 with Pyridine

Poynder¹,

Orue²,

_³

et al. 2021

Preprint

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<div>It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not displace chloride, but rather forms a weak complex with the iodine via halogen bonding along the C-I bond axis. This interaction is investigated by NMR, structural, charge density and theoretical investigations, which all indicate the pyridine does not activate PhICl2 as proposed.</div><div><br></div>

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Section: Resultsmentioning

confidence: 98%

On the Activation of PhICl2 with Pyridine

Poynder¹,

Orue²,

_³

et al. 2021

Preprint

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“…375 More recently, Wilson, Dutton et al reported the formation of the [I(bpy) Cl 2 ][ICl 4 ] complex, which contained a formal [ICl 2 ] + species. 376 The complex was fairly stable in the solid state, but highly reactive in solution; this behavior was used, e.g., for the oxidative chlorination of Au I -NHC complexes. Based on these results, one might conclude that the formation of related complexes with tpy is feasible, though not yet demonstrated.…”

Section: Terpyridine Complexes Of Pnictide Ions (Group 15)mentioning

confidence: 99%

The chemistry of the s- and p-block elements with 2,2′:6′,2′′-terpyridine ligands

Winter,

Newkome,

Schubert

2024

Inorg. Chem. Front.

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“…Planar molecules like XCl 4 – (X = Br, I) have a negative π-/p-hole on the surface of the halogen atom X, which is orthogonal to the molecular plane. These molecular entities may offer themselves as HaBAs for interacting HaBDs in many crystals.…”

Section: Halogen’s π-/P-hole On Covalently Bonded Halogen In Moleculesmentioning

confidence: 99%

Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit

Varadwaj,

Marques

et al. 2024

Crystal Growth & Design

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that fail to include the fundamental, underlying concept of (electrophilic) σand p-/π-hole theory and orbital-based charge transfer interactions that accompany halogen bond formation. An electrophilic σ-hole, or p-/π-hole, is an electron-density-deficient region of positive polarity (and positive potential) on the electrostatic surface on the side of halogen along, or orthogonal to, a covalently bonded halogen in a molecular entity that leads to the development of a noncovalent interaction�a halogen bond� when in close proximity to an electron-density-rich nucleophilic region on the same or another identical or different molecular entity, with which it interacts. This Article re-examines the characteristic features of the halogen bond and lists a wide variety of donors and acceptors that participate in halogen bonding. We add caveats that are essential for identifying halogen bonding in chemical systems, necessary for the appropriate use of the terminologies involved. Illustrative examples of chemical systems that feature inter-and intramolecular halogen bonds and other noncovalent interactions in the crystalline phase are given, together with a case study of some dimer systems using first-principles calculations. We also point out that the π-hole/belt (or p-hole/belt) that may develop on the surface of a halogen derivative in halogenated molecules may be prone to forming a π-hole/belt (or p-hole/belt) halogen bond when in close proximity to nucleophiles on another similar or different molecular entity.

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A 2,2′-bipyridine coordination complex of [ICl₂]⁺

Cited by 7 publications

References 36 publications

On the Activation of PhICl2 with Pyridine

On the Activation of PhICl2 with Pyridine

The chemistry of the s- and p-block elements with 2,2′:6′,2′′-terpyridine ligands

Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit

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A 2,2′-bipyridine coordination complex of [ICl2]+

Cited by 7 publications

References 36 publications

On the Activation of PhICl2 with Pyridine

On the Activation of PhICl2 with Pyridine

The chemistry of the s- and p-block elements with 2,2′:6′,2′′-terpyridine ligands

Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit

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Product

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A 2,2′-bipyridine coordination complex of [ICl₂]⁺