Diphenyldichlorophosphonium Trichloride−Chlorine Solvate 1:1, [PPh₂Cl₂]⁺Cl₃^-·Cl₂:  An Ionic Form of Diphenyltrichlorophosphorane. Crystal Structures of [PPh₂Cl₂]⁺Cl₃^-·Cl₂ and [(PPh₂Cl₂)⁺]₂[InCl₅]^2-

Abstract

An ionic form of diphenyltrichlorophosphorane, namely, diphenyldichlorophosphonium trichloride isolated as a dichlorine solvate (1), was obtained by treating PPh(2)Cl(3) with excess chlorine. The identity of this species was established by single-crystal X-ray analysis and (31)P, (1)H, and (35)Cl NMR and Raman spectra. Bis(diphenyldichlorophosphonium) pentachloroindate (2) was obtained by the reaction of diphenyltrichlorophosphorane with indium trichloride in dichloromethane for comparison purposes. Its identity was determined by (31)P NMR spectra and single-crystal X-ray analysis.

A 2D Polychloride Network Held Together by Halogen–Halogen Interactions

“…[12] Another intense broad Raman band centered at 465 cm À1 (calc.454 cm À1 )isassigned to the stretching mode of one Cl 2 unit. [11,12] Furthermore,w ef ound al ess intense Raman band at 420 cm À1 (calc. 424 cm À1 )that can be assigned to the Cl-Cl stretching mode of the other Cl 2 unit.…”

“…[11] In the crystal, this anion consists of a [ Cl 3 ] À anion with aw eakly coordinated Cl 2 molecule forming an irregularly shaped "hockey-stick"-like motif (C s ). This differs from quantumchemical calculations of isolated [Cl 5 ] À ,w hich predict ar egular V-shaped equilibrium structure (C 2v )s imilar to that observed in the crystal structures of the related pentahalides of bromine and iodine.…”

Theoretical investigation on charge‐assisted halogen bonding interactions in the complexes of bromocarbons with some anions

“…Such interactions, termed as charge‐assisted halogen bonds, are indeed of vital importance in crystal engineering. For example, halogen···halide (CY···X − , X and YCl, Br or I) synthons do play a crucial role in determining the crystal structure of halogenated pyridinium salts 31–35 and other crystal structures, such as diphenyl dichlorophosphonium trichloride‐chlorine solvate mixture 36, tetrahalometalate (II) ions 37–41, and 1,2‐dibromohexafluoropropane 42. More recently, Willett and coworkers described the role of C—Br···X − synthons in the crystal structures of Cu( n bp) 2 X 2 ( n bp = n ‐bromopyridine; n = 2 and 3) 43.…”

Ein durch Halogen‐Halogen‐Wechselwirkungen zusammengehaltenes 2D‐Polychloridnetzwerk

“…[11] Eine zusätzliche Cl 2 -Einheit (6-7) koordinert end-on orthogonal zur Kette.D iese Koordination ist bedeutend stärker (255.7(6) pm) als die der verbrückenden Einheiten und kann so auch als verzerrtes…”