S. A. Cooke

Pre-reactive complexes in mixtures of water vapour with halogens: characterisation of H2O...ClF and H2O...F2 by a combination of rotational spectroscopy and ab initio calculations.

Complexes H2O...ClF and H2O...F2 were detected by means of their ground-state rotational spectra in mixtures of water vapour with chlorine monofluoride and difluorine, respectively. A fast-mixing nozzle was used in conjunction with a pulsed-jet, Fourier-transform microwave spectrometer to preclude the vigorous chemical reaction that these dihalogen species undergo with water. The ground-state spectra of seven isotopomers (H2 16O...35ClF, H2 16O...ClF, H2 18O...35ClF, D2 16O... 35ClF, D2 16O...37ClF, HDO...35ClF and HDO...37ClF) of the ClF complex and five isotopomers (H2O...F2, H2 18O...F2, D2O...F2, D2 18O...Fi and HDO...F2) of the F2 complex were analysed to yield rotational constants, quartic centrifugal distortion constants and nuclear hyperfine coupling constants. These spectroscopic constants were interpreted with the aid of simple models of the complexes to give effective geometries and intermolecular stretching force constants. Isotopic substitution showed that in each complex the H2O molecule acts as the electron donor and either CIF or F2 acts as the electron acceptor, with nuclei in the order H2O...ClF or H2O...F2. For H2O...ClF, the angle phi between the bisector of the HOH angle and the O...Cl internuclear line has the value 58.9(16)degrees, while the distance r(O...Cl)= 2.6081(23) A. The corresponding quantities for H2O...F2 are phi = 48.5(21)degrees and r(O...Fi) = 2.7480(27) A, where Fi indicates the inner F atom. The potential energy V(phi) as a function of the angle phi was obtained from ab initio calculations at the aug-cc-pVDZ/MP2 level of theory for each complex by carrying out geometry optimisations at fixed values of phi in the range +/-80degrees. The global minimum corresponded to a complex of Cs symmetry with a pyramidal configuration at O in each. The function V(phi) was of the double-minimum type in each case with equilibrium values phie = +/-55.8degrees and +/-40.5degrees for H2O...ClF and H2O...F2, respectively. The barrier at the planar C2v conformation was V0= 174cm(-1) for H2O...ClF and 7cm(-1) for H2O...F2. For the latter complex, the zero-point energy level lies above the top of the barrier.

Rotational spectrum of thiophene···HCl Does thiophene act as an aromatic π-type electron donor or an n-type electron donor in hydrogen-bond formation?

The rotational spectra of the four isotopomers [32S]-thiophene···H35Cl, [32S]-thiophene···H37Cl, [32S]-thiophene···D35Cl and [34S]-thiophene···H35Cl of a complex formed between thiophene and hydrogen chloride have been observed by using a pulsed-nozzle, Fourier-transform microwave spectrometer. Rotational constants, centrifugal distortion constants and Cl-nuclear quadrupole coupling constants χaa, χbb-χcc and χab were determined. Interpretation of the spectroscopic constants led to the conclusion that the observed complex has Cs symmetry, with the Cl atom of HCl lying almost directly above the centre of mass of the thiophene ring but with the H atom of HCl pointing at the π-electron density near to the S atom. The S···H–Cl nuclei are almost collinear [ϑ=0.9(6)°] but the relatively large distance r(S···H)=2.7474(29) A indicates that the S···H interaction is weak. The angle φ between the C2 axis of thiophene and the S···H internuclear line was found to be 64.53(16)°. The distance r(*···Cl)=3.693 A from the centre of mass (*) of the thiophene ring to Cl and the angle (S*Cl)=98.9° are very similar in magnitude to the corresponding quantities in thiophene···Ar. Indeed, a comparison of thiophene···Ar, thiophene···HCl, benzene···Ar and benzene···HCl revealed a strong family relationship between the geometries of these four complexes. It is concluded that the non-bonding electron pair carried by S in thiophene is so weakly nucleophilic that when thiophene forms a hydrogen bond with HCl it does so via the aromatic π-electron system. In this respect, thiophene resembles benzene and is in stark contrast to its oxygen analogue, furan, with which HCl forms a hydrogen-bonded complex of C2v symmetry via the non-bonding electron pair on O.

The rotational spectrum of the benzene hydrogen bromide complex

Abstract Ground-state rotational spectra of six symmetric-top isotopomers, C 6 H 6 ⋯ H 79 Br, C 6 H 6 ⋯ H 81 Br, C 6 D 6 ⋯ H 79 Br, C 6 D 6 ⋯ H 81 Br, C 6 H 6 ⋯ D 79 Br and C 6 H 6 ⋯ D 81 Br, of the benzene-hydrogen bromide complex were observed and analysed to give the rotational constant B 0 , the centrifugal distortion constants D J and D JK , and the Br nuclear quadrupole and spin-rotation coupling constants X aa and M bb in each case. It is concluded that in the zero-point state the complex has effective C 6v symmetry, with HBr oriented so that H lies closest to the benzene ring and undergoes a circular motion which allows it to sample the π-electron density of the ring.

Angular geometries of complexes containing the O⋯Cl–F linkage: Rotational spectrum of formaldehyde⋯chlorine monofluoride

Ground-state rotational spectra of the three isotopomers H2CO⋯35ClF, H2CO⋯37ClF and D2CO⋯35ClF of a complex formed by formaldehyde and chlorine monofluoride were observed with a Balle–Flygare, Fourier-transform microwave spectrometer. A fast-mixing nozzle, specially modified to generate a continuous supply of H2CO from paraformaldehyde in situ close to the nozzle exit, was used to preclude the chemical reaction of H2CO and ClF. The rotational constants A0, B0, and C0, centrifugal distortion constants ΔJ, ΔJK, and δJ, components χaa, χbb−χcc, χab of the Cl-nuclear quadrupole tensor, and the spin–rotation coupling constant 1/2(Mbb+Mcc) were determined. Interpretation of the spectroscopic constants led to the conclusion that H2CO⋯ClF is a planar complex of Cs symmetry with r(O⋯Cl)=2.523(7) A, with an angle 180−φ=69.1(7)° between the C2 axis of H2CO and the O⋯Cl internuclear line, but with a deviation θ of the O⋯Cl–F nuclei from collinearity of only 3.2(7)°. A family relationship between the angular geometrie...

Rotational spectrum of thiophene⋯ClF and the role of thiophene as a π- or n-electron pair donor in weakly bound complexes

Abstract Rotational constants, centrifugal distortion constants and all five independent components χaa, χbb−χcc, χab, χac and χbc of the Cl nuclear quadrupole coupling tensor χαβ have been determined for thiophene⋯ 35 ClF and thiophene⋯ 37 ClF . A method for determining the geometry of this complex of C1 symmetry is presented which uses the direction cosines θaz, θbz and θcz (z is the ClF axis), determined by diagonalisation of the χαβ tensor, in combination with principal moments of inertia. Four geometries of thiophene⋯ClF are consistent with the observed quantities, but each has ClF interacting with the π-electron system on one face of the thiophene ring.

Interaction of benzene and halogens in the gas-phase: rotational spectrum of C6H6···ClF

Ground-state rotational spectra of three isotopomers, C6H6···35ClF, C6H6···37ClF and C6D6···35ClF, of a complex formed by benzene with chlorine monofluoride have been observed by pulsed-nozzle, Fourier-transform microwave spectroscopy. Chemical reaction between the two components was precluded by use of a fast-mixing nozzle. A vibrational satellite associated with a low lying state (v=1) was also observed for the C6H6···35ClF and C6D6···35ClF isotopomers. The spectra were established to be of the symmetric-top type, but with large centrifugal distortion effects associated both with the frequencies of the unperturbed line centres and with the Cl nuclear quadrupole hyperfine structure. In the ground state, these effects were reflected in a large centrifugal distortion constant DJK, in higher order distortion constants of significant magnitude, and in a strong dependence of the Cl nuclear quadrupole coupling constant on the quantum number K. In the v=1 state, the constant DJK and the centrifugal distortion terms χK and χD that affect the nuclear quadrupole hyperfine structure were a similar magnitude to those of the v=0 state, but of opposite sign. The nuclear quadrupole coupling constants, χR, appropriate to the J=0, K=0 states, and the changes in the rotational constants B0 with isotopic substitution, were interpreted in terms of a model for the complex in which, at equilibrium, the ClF axis is inclined at an angle ϑ≈14° to the C6 axis of benzene, with the two axes intersecting at the ClF centre of mass. The Cl atom lies closer to the benzene ring than does the F atom. The extrapolation of the ClF internuclear axis intersects the plane of the benzene ring at a point (*) that lies at a distance of ca. 0.24 Ainside the ring from the centre of a C–C bond. The conformation with ϑ=0° (ClF axis and benzene C6 axis coincident) corresponds to a potential energy maximum, concentric with which is an approximately circular valley corresponding to ϑ≈14°. This type of potential energy surface is consistent with the symmetric-top nature of the observed spectra, with the relatively small energy separation of the v=0 and v=1 states, and with large, but oppositely signed, centrifugal distortion effects in the two states originating in a Coriolis interaction between them. The distance r(*···Cl)=3.313 Awas also determined.

Rotational spectrum and properties of a gas-phase complex of molecular fluorine and hydrogen cyanide

Abstract Ground-state rotational spectra of three isotopomers HC14N … F2, HC15N … F2 and DC14N … F2 of a complex formed by hydrogen cyanide and molecular fluorine were observed by using a fast-mixing nozzle in a Fourier transform microwave spectrometer. Effects of F-F spin-spin and F-spin rotation coupling were observed in the spectra of HC15N … F2 and HC14N … F2 and allowed for in the analysis. Spectroscopic constants B0, DJ and ξaa(14N) appropriate to a linear molecule HCN … F2 were determined and interpreted in terms of the geometry and binding strength of the complex. Properties of several axially symmetric complexe involving the N … X2 weak bond (X = F or Cl) are compared.

Evidence concerning the relative nucleophilicities of non-bonding and π-bonding electrons in furan from the rotational spectrum of furan···ClF

The rotational spectra of the three isotopomers C4H4O···35ClF, C4H4O···37ClF and C4D4O···35ClF of a complex formed between furan and chlorine monofluoride have been observed by means of a pulsed-nozzle, Fourier-transform microwave spectrometer fitted with a fast-mixing nozzle to preclude any chemical reaction among the component gases. Transitions allowed by all three components µa, µb and µc of the electric dipole moment were observed, those associated with µc exhibiting a small doubling (ca. 20 kHz). Spectral analysis yielded rotational constants, centrifugal distortion constants and (for the isotopomers C4H4O···35ClF and C4H4O···37ClF) all five independent components of the Cl nuclear quadrupole coupling tensor χαβ (α, β = a, b, c). Diagonalisation of the tensor χαβ led to the values of the components χii (i = x, y, z) in the ClF principal axis system and the direction cosines θαz (α = a, b, c) relating the ClF axis (z) to the principal inertial axis system. The geometry obtained by fitting the principal moments of inertia of the three observed isotopomers is consistent with the θαz values and has the ClF subunit approximately perpendicular to one of the C(2)–C(3) bonds of furan. The end δ+Cl of ClF thus appears to interact with the π electron density between these two atoms. The distance of the Cl atom from the point of intersection of the extrapolated ClF axis with the ring is r(···Cl) = 2.726 A. The doubling of the c-type transitions is interpreted in terms of a motion in which the interaction switches from C(2)–C(3) to C(2′)–C(3′). The contrast between the angular geometries of furan···HCl and furan···ClF is discussed in the context of the relative nucleophilicities of the n-pair and the aromatic π-electrons of furan.

IS PYRIDINIUM HYDROCHLORIDE A SIMPLE HYDROGEN-BONDED COMPLEX C5H5N...HCL OR AN ION PAIR C5H5NH+...CL- IN THE GAS PHASE ? AN ANSWER FROM ITS ROTATIONAL SPECTRUM

The ground-state rotational spectra of the three isotopomers C5H514N···H35Cl, C5H514N···H37Cl and C5H514N···D35Cl of a complex formed by pyridine with hydrogen chloride have been observed by using a fast-mixing nozzle in combination with a pulsed-nozzle, FT microwave spectrometer. Rotational constants A0, B0, C0, centrifugal distortion constants, ΔJ, ΔJK, δJ, δK and nuclear quadrupole coupling constants χaa(A) and χbb(A) − χcc(A) (where A = 14N or Cl) were determined in each case. A detailed interpretation of the spectroscopic constants led to the conclusion that the observed complex has a planar, C2v geometry, with the HCl subunit forming a hydrogen bond to N and lying along the C2 axis of pyridine. The nitrogen to chlorine distance was determined to be 2.999(2) A. The magnitudes of the nuclear quadrupole coupling constants χaa(A) and the intermolecular stretching force constants kσ in comparison with those expected in the hydrogen-bond C5H5N···HCl and ion-pair C5H5NH+···Cl− limits show that the extent of proton transfer from HCl to pyridine is small.

Rotational spectrum and molecular properties of the dinitrogen–chlorine monofluoride complex

The ground-state rotational spectra of the three isotopomers 14N2⋯35ClF, 15N2⋯35ClF and 15N2⋯37ClF of a complex formed by dinitrogen and chlorine monofluoride have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The spectroscopic constants B0, DJ, χaa(A)(A =14Ni, 14No or Cl) and Mbb(Cl) are reported. The complex is shown to have a linear (or nearly linear) arrangement NoNi⋯ClF of the nuclei in the equilibrium conformation with r(Ni⋯Cl)= 2.920(2)A. The intermolecular stretching force constant, kσ= 5.00(5) N m–1, is implied by the centrifugal distortion constant DJ. Interpretation of the nuclear quadrupole coupling constants χaa(A) leads to the oscillation angles θav= cos–1〈cos2θ〉1/2= 17.8(5)° and ϕav= cos–1〈cos2θ〉1/2= 10(3)° for the N2 and ClF subunits, respectively. Additionally, the diffence χaa(Ni)–χaa(No) leads, on the basis of a simple model, to the conclusion that the polarisation of N2 attending complex formation is equivalent to the transfer of a fraction δ≈ 0.02 of an electronic charge from No to Ni. A comparison of the properties of four related complexes N2⋯YF and OC⋯YF, where Y = Cl or H, is presented.