31P CP-MAS NMR, Vibrational, and X-Ray Characterization of the Adducts of Triphenylphosphine Sulfide with ICl and IBr

Reactions Between Chalcogen Donors and Dihalogens/Interalogens: Typology of Products and Their Characterization by FT‐Raman Spectroscopy

“…Those obtained from molecules containing selenium and diiodine are less numerous [14, 25, 69–81], while few adducts of - and -donors with [57–60, 62–67, 81–83] and [60, 61, 67, 68, 83, 84] have been reported and structurally characterized in the literature. Three adducts of -donors have been characterized by X-ray diffraction analysis [65, 94], and no CT adducts of -donors are known with any dihalogen or interhalogen.…”

“…adducts with both - and -donors show one main peak in their FT-Raman spectra in the range 190–140 cm −1 [16, 59, 60, 62–67, 81] at a lower frequency with respect to solid [216 cm −1 , d (I−Br) = 2.521(4) Å] [98], and it is assignable to a stretching vibration of the E−I−Br three-body system having a major contribution from the ν (I−Br) vibration [63]. adducts (only four out of seven are both structurally and vibrationally characterized) [60, 67, 68] generally show in their FT-Raman spectra two main peaks: one in the range 240–180 cm −1 presumably due to the antisymmetric ( ν 3 ) stretching vibration of the E−I−Cl three body-system ( = , ), and the other at about 130 cm −1 due to the symmetric ( ν 1 ) stretching vibration (solid is characterized by a single peak at 283 cm −1 in its FT-Raman spectrum with a d (I−Cl) = 2.446(6) Å) [99]. Interestingly, by considering the Δ d (I−Y) parameter ( = , , ), a linear correlation appears also to exist between Δ d (I−Br) and ν (I−Br) for adducts, and between Δ d (I−Cl) and the ν (E−I−Cl) stretching mode corresponding to the ν antisym in symmetric three-body systems, for adducts (Figure 8).…”

“…Scatter plot of Δ d (I−Y) [Δ d (I−Y) = d (I−Y) adduct − d 0 (I−Y) gas phase ( = , , )] versus d (S−I) [ = (⋄) [5, 11–44, 46–61], (Δ) [57–60, 62–67, 81–83], (o) [60, 61, 67, 68, 83, 84]; d 0 (I−I) gas phase = 2.67 Å [95], d 0 () gas phase = 2.47 Å [95], d 0 () gas phase = 2.32 Å [95]]; benzimidazole-2(3)-thione · (□) [45]. …”

“…Scatter plot of ν (I−I)/cm −1 versus d (I−I)/ Å for weak or medium-weak adducts (⋄, data from [13, 14, 17–19, 21, 22, 25, 28, 30–33, 39, 43–46, 48, 54–56, 59, 60, 67]), solid diiodine (∗) [97]. …”

“…Scatter plot of ν (I−Y)/cm −1 versus Δ d (I−Y)/ Å [=(⋄) [13, 14, 17–19, 21, 22, 25, 28, 30–33, 39, 43–46, 48, 54–56, 59, 60, 67], (Δ) [6, 59, 60, 62–67, 81], (o) [60, 67, 68]]. ∗ = solid diiodine [97], × = solid [98], + = solid [99].…”