Inter- and intramolecular electron transfer in the complex OC···ICl determined from iodine and chlorine nuclear quadrupole hyperfine structure in its rotational spectrum

Davey, J. B.; Legon, A. C.; Waclawik, Eric R.

doi:10.1039/a903182k

Cited by 31 publications

(31 citation statements)

References 21 publications

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“…[9,14,15,21,22] To our knowledge, no CO/IF complex has been reported so far. The high instability of IF does not allow its handling in the gas phase and therefore co-deposition of CO and IF in a matrix has not been possible.…”

Section: Matrix Photochemistry Of Fc(o)i: Photoisomerization Of Matrimentioning

confidence: 82%

Molecular Structure, Spectroscopy and Matrix Photochemistry of Fluorocarbonyl Iodide, FC(O)I

Chiappero

Argüello

García

et al. 2004

Chemistry A European J

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The molecular structure of FC(O)I has been determined by gas electron diffraction. High-level ab initio methods, including coupled-cluster and the new correlation-consistent basis sets for fourth row elements, have been used to calculate the structure of FC(O)I. A comprehensive vibrational spectroscopic study (both IR and Raman) complemented by high-level calculations has also been performed. Furthermore, UV, mass, and NMR spectra have been recorded for FC(O)I. The matrix photochemistry of FC(O)I has been studied with a low-pressure mercury lamp and with a high-pressure xenon lamp in combination with interference and cut-off filters. UV photolysis revealed the formation of the OC. IF and OC.FI complexes and further photolysis of these complexes at lambda>320 nm resulted in a re-formation of FC(O)I. The structural conformation of the complexes has been characterized by comparing shifts in their CO and IF vibrational modes with respect to those of the free species. The structures, vibrational properties, and stability of the complexes were analyzed with the aid of coupled-cluster ab initio calculations.

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Section: Matrix Photochemistry Of Fc(o)i: Photoisomerization Of Matrimentioning

confidence: 82%

Molecular Structure, Spectroscopy and Matrix Photochemistry of Fluorocarbonyl Iodide, FC(O)I

Chiappero

Argüello

García

et al. 2004

Chemistry A European J

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“…On the other hand, the majority of gas-phase investigations so far have involved the rotational spectroscopy of homo-and hetero-nuclear dihalogen molecules XY = F 2 , ClF, Cl 2 , BrCl, Br 2 , or ICl as the halogen-atom donor (or electron acceptor) interacting with a wide variety of simple Lewis bases as the halogen-bond acceptor (or electron donor). [2][3][4][6][7][8][9][10][11][12][13][14][15] The systematic variation of B and XY revealed patterns among the various properties so determined and these patterns have led to several generalisations, among which are included some rules for accounting for angular geometry (the relative orientation of the two subunits), an assignment of electrophilicities of dihalogens XY and a simple relationship between the distance r(Z· · ·X) and the sum σ (Z) + σ (X) of the van der Waals radii of the acceptor atom Z of B and the halogen atom X. [2][3][4]19 It was found that the behaviour of the halogen bond in the B· · ·XY series is redolent of that of the hydrogen bond in the corresponding series B· · ·HX, suggesting a strong parallelism between halogen and hydrogen bonds; such a parallelism was also noted in the solid state.…”

Section: Discussionmentioning

confidence: 99%

“…The gas-phase investigations of the iodine bond have so far been restricted to complexes B· · ·ICl, in which ICl acts as the iodine donor. [6][7][8][9][10][11][12][13][14][15] The molecule I−CF 3 provides a bridge between solid-state investigations involving I−C 6 F 4 −I or I−(CF 2 ) n −I and the gas-phase studies of B· · ·ICl. Presumably, the electron-withdrawing power of the CF 3 group is less than that of a Cl atom and will lead to complexes B· · ·ICF 3 that are less strongly bound than B· · ·ICl, for a given B.…”

Section: Introductionmentioning

confidence: 99%

Rotational spectra and properties of complexes B⋯ICF3 (B = Kr or CO) and a comparison of the efficacy of ICl and ICF3 as iodine donors in halogen bond formation

Stephens

Walker

Legon

2011

The Journal of Chemical Physics

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The ground-state rotational spectra of two weakly bound complexes B···ICF(3) (B = Kr or CO) formed by trifluoroiodomethane have been observed in pulsed jets by using two types of Fourier-transform microwave spectroscopy (chirped-pulse and Fabry-Perot cavity). Both complexes exhibit symmetric-top type spectra, thus indicating that the Kr atom in Kr···ICF(3) and both the C and O atoms in OC···ICF(3) lie along the C(3) axis of ICF(3). The rotational constant B(0), the centrifugal distortion constants D(J) and D(JK), and the iodine nuclear quadrupole coupling constant χ(aa)(I) were determined for each of the isotopologues (84)Kr···ICF(3), (86)Kr···ICF(3), (16)O(12)C···ICF(3), (16)O(13)C···ICF(3), and (18)O(12)C···ICF(3). Interpretation of the spectroscopic constants reveals that the carbon atom of CO is adjacent to I and participates in the weak bond in OC···ICF(3). Simple models based on unperturbed component geometries lead to the distances r(Kr···I) = 3.830(1) Å and r(C···I) = 3.428(1) Å in Kr···ICF(3) and OC···ICF(3), respectively, and to the quadratic force constants for stretching of the weak bond k(σ) = 2.80 N m(-1) and 3.96 N m(-1), respectively. The distances r(Z···I) (Z is the acceptor atom in B), the k(σ) values, and the angular geometries of the pair of complexes B···ICF(3) and B···ICl for a given B are compared when B = Kr, CO, H(2)O, H(2)S, or NH(3). The comparison reveals that the iodine bond in B···ICF(3) is systematically longer and weaker than that of B···ICl, while the angular geometry of the B···I moiety is isomorphic in B···ICF(3) and B···ICl for a given B. It is concluded that -CF(3) is less effective than -Cl as an electron-withdrawing group when attached to an I atom and that the angular geometries of the B···ICF(3) can be predicted by means of a simple rule that holds for many hydrogen- and halogen-bonded complexes.

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“…Since this review was submitted the rotational spectra of the series of complexes B´´´ICl (B Ar, [175] CO, [176] C 2 H 2 , [177] C 2 H 4 , [178] H 2 O, [179] H 2 S, [180] NH 3 [181] ) have been detected and analyzed. Table 14 displays the properties r(Z´´´I), k s , d 1 , and d 2 , as determined from the spectroscopic constants (see Section 2.1).…”

Section: Addendummentioning

confidence: 99%

“…The values of d 1 and d 2 in Table 14 were obtained by using the appropriate forms of Equation (8) and (9) (Section 3.1.2), that is, with d in Equation (8) replaced by (d 1 À d 2 ) and d in Equation (9) replaced by d 2 (see reference [176] for the detailed arguments). It was found that if the reasonable assumption d 1 0.0 is made for the weakly bound complex Aŕ´´I Cl, the result is d 2 5.4(1) Â 10 À3 and f av 5.45(1)8.…”

Section: Addendummentioning

confidence: 99%

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Legon

1999

Angew. Chem. Int. Ed.

637

443

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Similar and yet also notably different are the B small middle dot small middle dot small middle dotXY and B small middle dot small middle dot small middle dotHX complexes in the gas phase, where B is a simple Lewis base, XY is a homo- or heterodihalogen molecule, and HX is a hydrogen halide. This is demonstrated, for example, by the structures of oxirane small middle dot small middle dot small middle dotClF and oxirane small middle dot small middle dot small middle dotHCl (see picture). Both bonds are dominated by simple electrostatic interactions, but differ in terms of their propensity for nonlinearity.

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Inter- and intramolecular electron transfer in the complex OC···ICl determined from iodine and chlorine nuclear quadrupole hyperfine structure in its rotational spectrum

Cited by 31 publications

References 21 publications

Molecular Structure, Spectroscopy and Matrix Photochemistry of Fluorocarbonyl Iodide, FC(O)I

Molecular Structure, Spectroscopy and Matrix Photochemistry of Fluorocarbonyl Iodide, FC(O)I

Rotational spectra and properties of complexes B⋯ICF3 (B = Kr or CO) and a comparison of the efficacy of ICl and ICF3 as iodine donors in halogen bond formation

Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

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