Anion-π interaction with alkenes: persistent complexes vs. irreversible reactions of anions with tetracyanoethylene.

The interaction of the tetracyanoethylene (TCNE) π-acceptor with oxo- and fluoro-anions (BF4-, PF6-, ClO4-, NO3-) led to the formation of anion-π complexes in which these polyatomic anions were located over the face of alkenes, with multiple contacts being shorter than the van der Waals separations. The anion-π associations of TCNE with halides were delimited by the electron-donor strengths and nucleophilicity of the anions. Specifically, while bromides formed persistent anion-π associations with TCNE in the solid state and in solutions, only transient anion-π complexes with iodides and chlorides were observed. In the case of iodide (strong 1e reducing agent), the formation of anion-π complexes was followed by the reduction of the π-acceptor to the TCNE-˙ anion-radical. The interaction of TCNE with Cl- (and F-) anions (which are better nucleophiles in the aprotic solvents) led to the formation of 1,1,2,3,3-pentacyanoprop-2-en-1-ide anions. Thermodynamics, UV-Vis spectra, and structures, as well as contributions of electrostatics, orbital interactions, and dispersion to the interaction energies in the complexes of TCNE with various anions were closely related to the characteristics of the corresponding associations with the aromatic and p-benzoquinone acceptors. This points out the general equivalence of the interactions in the anion-π complexes with different π-acceptors and the critical role of the nature of the anions in these bindings.

Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor-Acceptor Bonding.

4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide's oxygen atom to Lewis acids on multicenter donor-acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides' oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the formation of dark co-crystals comprising π-stacked Zn-coordinated N-oxides and pyrene similar to that found with protonated or (reported earlier) BF3-bonded N-oxides. Computational studies indicated that the coordination of N-oxides to zinc(II), BF3, or protonation led to the strengthening of the multicenter bonding of the nitro-heterocycle with pyrene, and this effect was related both to the increased electrostatic attraction and molecular-orbital interactions in their complexes.

Halogen Bonding and/or Covalent Bond: Analogy of 3c-4e N···I···X (X = Cl, Br, I, and N) Interactions in Neutral, Cationic, and Anionic Complexes.

X-ray structural measurements and computational analysis demonstrated the similarity of the geometries and electronic structures of the X-I···N (X = Cl, Br, I, and N) bonding in strong halogen-bonded (HaB) complexes and in the anionic or cationic halonium ions. In particular, I···N bond lengths in the solid-state associations formed by strong HaB donors (e.g., I2, IBr, ICl, and N-iodosuccinimide) and acceptors (e.g., quinuclidine or pyridines) were in the same range of 2.3 ± 0.1 Å as those in the halonium ions [e.g., the bis(quinuclidine)iodonium cation or the 1,1'-iodanylbis(pyrrolidine-2,5-dione) anion]. In all cases, bond lengths were much closer to those of the N-I covalent bond than to the van der Waals separations of these atoms. The strong N···I bonding in the HaB complexes led to a substantial charge transfer, lengthening and weakening of the I···X bonds, and polarization of the HaB donors. As a result, the central iodine atoms in the strong HaB complexes bear partial positive charges akin to those in the halonium ions. The energies and Mayer bond orders for both N···I and I···X bonds in such associations are also comparable to those in the halonium ions. The similarity of the bonding in such complexes and in halonium ions was further supported by the analysis of electron densities and energies at bond critical (3, -1) points in the framework of the quantum theory of atoms in molecules and by the density overlap region indicator. Overall, all these data point out the analogy of the symmetric N···I···N bonding in the halonium ions and the asymmetric X···I···N bonding in the strong HaB complexes, as well as the weakly covalent character of these 3c-4e interactions.

Exploring the Nature of Anion-π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides.

The variations in the nature and properties of the anion-π complexes with different types of anions are identified via experimental (UV-vis and X-ray crystallographic) measurements and computational analysis of the associations of tetracyanopyrazine, tetrafluoro-, or dichlorodicyano-p-benzoquinone. Co-crystals of these π-acceptors with the salts of fluoro- and oxoanions (PF6-, BF4-, CF3SO3-, or ClO4-) comprised anion-π bonded alternating chains or 1:2 complexes showing interatomic contacts of up to 15% shorter than the van der Waals separations. DFT computations confirmed that binding energies between the neutral π-acceptors and polyatomic noncoordinating oxo- and fluoroanions are comparable to those in the previously reported anion-π complexes with more nucleophilic halides. Yet, while the latter show distinct charge-transfer bands in the UV-vis range, the absorption spectra of the solutions containing oxo- and fluoroanions and the π-acceptors were close to those of the individual reactants. The natural bond orbital (NBO) analysis revealed a very small charge transfer of Δq = 0.01-0.02 e in the complexes with oxo- or fluoroanions as compared to the Δq = 0.05-0.22 e found for analogous complexes with halides. These distinctions were related to the smaller frontier orbital energy gap and better overlap in the complexes with halides (since the highest occupied orbitals of these monoatomic anions are closer in energy to the lowest unoccupied orbitals of the π-acceptors) as compared to that in the multicenter-bonded associations with polyatomic oxo- and fluoroanions. In accordance with these data, the energy decomposition analysis showed that while the complexes of neutral π-acceptors with the fluoro- and oxoanions are formed predominantly via electrostatic interaction, the associations with halides comprised significant orbital (charge-transfer) interactions and they explain their spectral and structural features.

From weak to strong interactions: structural and electron topology analysis of the continuum from the supramolecular chalcogen bonding to covalent bonds.

The relationship between covalent and supramolecular bonding, and the criteria of the assignments of different interactions were explored via the review of selenium and tellurium containing structures in the Cambridge Structural Database and their computational analysis using Quantum Theory of Atoms in Molecules (QTAIM). This combined study revealed continuums of the interatomic Se⋯Br and Te⋯I distances, dCh⋯X, in the series of associations from the sums of the van der Waals radii of these atoms (rCh + rX) to their covalent bond lengths. The electron densities, ρ(r), at Bond Critical Points (BCPs) along the chalcogen bond paths increased gradually from about 0.01 a.u. common for the non-covalent interactions to about 0.1 a.u. typical for the covalent bonds. The log ρ(r) values fell on the same linear trend line when plotted against normalized interatomic distances, RXY = dCh⋯X/(rCh + rX). The transition from the positive to negative values of the energy densities, H(r), at the BCPs (related to a changeover of essentially non-covalent into partially covalent interactions) were observed at RXY ≈ 0.80. Synchronous changes of bonding characteristics with RXY (similar to that found earlier in the halogen-bonded systems) designated normalized interatomic separation as a critical factor determining the nature of these bondings. The uninterrupted continuums of Te⋯I and Se⋯Br bond lengths and BCPs' characteristics signified an intrinsic link between limiting types of bonding involving chalcogen atoms and between covalent and supramolecular bonding in general.

Solvent and Ionic Atmosphere Effects in Anion-π Interactions: Complexes of Halide Anions with p-Benzoquinones.

The interplay between the solvent polarity and ionic atmosphere in anion-π association was evaluated via an experimental and a computational study of the BQ·X- complexes between benzoquinones (BQ) and halide anions (X-). The UV-Vis spectral measurements showed that these complexes are characterized by the strong absorption bands in the 300-450 nm range and their effective formation constants, Keff, measured in dichloromethane in the absence (or at low concentrations) of the supporting electrolyte, Bu4NPF6, were higher than those in acetonitrile. The experimental data were consistent with the results of the computations, which showed that magnitudes of the interaction energy, ΔE, between BQ and X- decreased considerably with the increase in the polarity of the media. The addition of auxiliary electrolytes (e.g., Bu4NPF6) led to a decrease in the concentration of the BQ·X- complexes. These changes were related to the competing associations of the π-acceptors with halides and PF6- anions (since the interaction energies between BQ acceptors and common non-halide anions, e.g., PF6-, BF4-, and NO3-, were comparable to those in the BQ·X- complexes) and to the increased ionic strength of the solutions. The variations in strength of anion-π interactions with the solvent polarity and ionic atmosphere were related to the higher effective ionic radii of the complexes. Due to the larger effects of the auxiliary electrolytes in dichloromethane, the formation constants for the BQ·X- complexes measured at high ionic strength in this solvent were lower than those in more polar acetonitrile or propylene carbonate. Such a combination of the effects of the solvent and ionic atmosphere should be taken into account when comparing experimental data with the results of the calculations and in design of the systems for molecular recognition and catalysis.

Thermodynamics and Spectroscopy of Halogen- and Hydrogen-Bonded Complexes of Haloforms with Aromatic and Aliphatic Amines.

Similarities and differences of halogen and hydrogen bonding were explored via UV-Vis and 1H NMR measurements, X-ray crystallography and computational analysis of the associations of CHX3 (X=I, Br, Cl) with aromatic (tetramethyl-p-phenylenediamine) and aliphatic (4-diazabicyclo[2,2,2]octane) amines. When the polarization of haloforms was taken into account, the strengths of these complexes followed the same correlation with the electrostatic potentials on the surfaces of the interacting atoms. However, their spectral properties were quite distinct. While the halogen-bonded complexes showed new intense absorption bands in the UV-Vis spectra, the absorptions of their hydrogen-bonded analogues were close to the superposition of the absorption of reactants. Additionally, halogen bonding led to a shift in the NMR signal of haloform protons to lower ppm values compared with the individual haloforms, whereas hydrogen bonding of CHX3 with aliphatic amines resulted in a shift in the opposite direction. The effects of hydrogen bonding with aromatic amines on the NMR spectra of haloforms were ambivalent. Titration of all CHX3 with these nucleophiles produced consistent shifts in their protons' signals to lower ppm values, whereas calculations of these pairs produced multiple hydrogen-bonded minima with similar structures and energies, but opposite directions of the NMR signals' shifts. Experimental and computational data were used for the evaluation of formation constants of some halogen- and hydrogen-bonded complexes between haloforms and amines co-existing in solutions.

"Anti-electrostatic" Halogen Bonding between Ions of Like Charge.

Halogen bonding occurs between molecules featuring Lewis acidic halogen substituents and Lewis bases. It is often rationalized as a predominantly electrostatic interaction and thus interactions between ions of like charge (e. g., of anionic halogen bond donors with halides) seem counter-intuitive. Herein, we provide an overview on such complexes. First, theoretical studies are described and their findings are compared. Next, experimental evidences are presented in the form of crystal structure database analyses, recent examples of strong "anti-electrostatic" halogen bonding in crystals, and the observation of such interactions also in solution. We then compare these complexes to select examples of "counter-intuitive" adducts formed by other interactions, like hydrogen bonding. Finally, we comment on key differences between charge-transfer and electrostatic polarization.

Effects of structural variations on π-dimer formation: long-distance multicenter bonding of cation-radicals of tetrathiafulvalene analogues.

The multicenter (pancake) bonding between cation-radicals of tetramethyltetraselenafulvalene, TMTSF+˙, tetramethyltetrathiafulvalene, TMTTF+˙, and bis(ethylenedithio)-tetrathiafulvalene, ET+,˙ was compared to that of tetrathiafulvalene, TTF+˙. To minimize counter-ion effects, the cation-radical salts with weakly coordinating anions (WCA), tetrakis(3,5-trifluoromethylphenyl)borate, dodecamethylcarborane and hexabromocarborane were prepared. Solid-state (X-ray and EPR) measurements revealed diamagnetic π-dimers in the TMTSF and ET salts and the separate monomers in the TTF salts with all WCAs, while TMTTF existed as a dimer in one and a monomer in two salts. The variable-temperature UV-Vis studies of these salts in solution showed that the thermodynamics of formation of the π-bonded dimers of TMTTF+˙ was close to that of TTF+˙, while TMTSF+˙ and ET+˙ showed a higher propensity for π-dimerization. These data indicated that the replacement of sulfur with heavier selenium or insertion of ethylenedithia-substituents into the TTF core increases the π-dimers' stability. Yet, computational analysis indicated that the weakly covalent component of π-bonding decreases in the order TTF > TMTTF > TMTSF > ET. The higher stability of the π-dimers of TMTSF+˙ and ET+˙ cation-radicals was related to a decrease of the electrostatic repulsion between cationic counter-parts and an increase of dispersion components in these associations.

Halogen Bonding Between Anions: Association of Anion Radicals of Tetraiodo-p-benzoquinone with Iodide Anions.

Halogen bonding between two negatively charged species, tetraiodo-p-benzoquinone anion radicals (I4 Q-. ) and iodide anions, was observed and characterized for the first time. X-ray structural and EPR/UV-Vis spectral studies revealed that the anion-anion bonding led to the formation of crystals comprising 2D layers of I4 Q-. anion radicals linked by iodides and separated by Et4 N+ counter-ions. Computational analysis suggested that the seemingly antielectrostatic halogen bonds in these systems were formed via a combination of several factors. First, an attenuation of the interionic repulsion by the solvent facilitated close approach of the anions leading to their mutual polarization. This resulted in the appearance of positively charged areas (σ-holes) on the surface of the iodine substituents in I4 Q-. responsible for the attractive interaction. Finally, the solid-state associations were also stabilized by multicenter (4:4) halogen bonding between I4 Q-. and iodide.

Anion-π Complexes of Halides with p-Benzoquinones: Structures, Thermodynamics, and Criteria of Charge Transfer to Electron Transfer Transition.

Interchange of complex formation and electron-transfer reactions between halide anions and p-benzoquinones were established via UV-vis spectral and X-ray structural measurements and computational analysis. Solution-phase interaction of the p-benzoquinone acceptors with Cl-, Br-, or I- donors led to the formation of anion-π complexes showing strong absorption bands in the UV-vis range. Formation constants and calculated interaction energies of these complexes increased, and donor/acceptor separations decreased with increasing reduction potentials of p-benzoquinones. Mulliken correlation and NBO analysis indicated a charge-transfer nature of these anion-π associates. Most notably, the increase of the acceptor strength led to a transition between the formation of the persistent anion-π complexes and electron-transfer reactions. Thermodynamic analysis accounted for the experimental observations of anion radicals and trihalide anions in solutions of p-benzoquinones with iodide or (for the strongest acceptor) bromide donors. Kinetics of these processes indicated that anion-π complexes represent critical intermediates of the redox reactions. In contrast to Cl-, Br-, or I- anions, interaction of p-benzoquinones with F- anions led to the formation of σ-complexes, and the appearance of anion radicals in such systems was related to the follow-up reactions of these complexes.

Complexes of Diiodine with Heteroaromatic N-Oxides: Effects of Halogen-Bond Acceptors in Halogen Bonding.

Halogen bonding (XB) in complexes of diiodine with heteroaromatic N-oxides was examined via a combination of UV-vis spectral and X-ray structural measurements, as well as computational analysis. While all of these associates were formed by analogous I···O bonds, they showed considerable variations of formation constants (5-1500 M-1) and intermolecular I···O bond length (2.3-3.2 Å). In the solid state, both atoms of I2 molecules were involved in XB, and the I···O separations were determined by the electron-donor abilities of N-oxides and the strength of the bonding on the opposite side of the ditopic XB donor. The solution-phase formation constants of 1:1 complexes, K, as well as magnitudes of the calculated interaction energies, ΔE, increased with the shift of the values of the most negative potentials on the surfaces of N-oxides' oxygen atoms, Vmin, toward more negative values. Yet, the interatomic contacts consistently deviated from the locations of Vmin. Instead, the structures of complexes were well suited for highest occupied molecular orbital/lowest unoccupied molecular orbital interactions of reactants. The values of K, ΔE, and the intermolecular distances dI···O in the calculated complexes were highly correlated with the charge-transfer interaction energies derived from the natural bond orbital analysis. This indicated that, besides electrostatic, molecular orbital interactions play a substantial role in XB between diiodine and N-oxides. This conclusion was supported by the analysis of the complexes using the quantum theory of atoms in molecules, noncovalent interaction index, and density overlap region indicator, which showed that the covalent character of I···O bonding increases with the rise of interaction energies in the complexes.

Molecular Bases for Anesthetic Agents: Halothane as a Halogen- and Hydrogen-Bond Donor.

Although instrumental for optimizing their pharmacological activity, a molecular understanding of the preferential interactions given by volatile anesthetics is quite poor. This paper confirms the ability of halothane to work as a hydrogen-bond (HB) donor and gives the first experimental proof that halothane also works as a halogen-bond (HaB) donor in the solid state and in solution. A halothane/hexamethylphosphortriamide co-crystal is described and its single-crystal X-ray structure shows short HaBs between bromine, or chlorine, and the phosphoryl oxygen. New UV/Vis absorption bands appear upon addition of diazabicyclooctane and tetra(n-butyl)ammonium iodide to halothane solutions, indicating that nitrogen atoms and anions may mediate the HaB-driven binding processes involving halothane as well. The ability of halothane to work as a bidentate/tridentate tecton by acting as a HaB and HB donor gives an atomic rationale for the eudismic ratio shown by this agent.

Resolving the halogen vs. hydrogen bonding dichotomy in solutions: intermolecular complexes of trihalomethanes with halide and pseudohalide anions.

Halogen- and hydrogen-bonded complexes between trihalomethanes, CHX3, and (pseudo-)halide anions, A-, co-existing in acetonitrile solutions were identified and characterized via a combination of UV-vis and NMR spectral measurements with the results of X-ray structural and computational analyses. Halogen-bonded [CHX3, A-] complexes displayed strong absorption bands in the UV range (showing Mulliken correlations with the frontier orbital energies of the interacting species) and a decreased shift of the NMR signal of trihalomethanes' protons. Hydrogen bonding led to the opposite (increased) NMR signal shift and the UV-vis absorption bands of the hydrogen-bonded [CHX3, A-] complexes were similar in intensity to those of the separate CHX3 molecules. The simultaneous multivariable treatment of the results of UV-vis and NMR titrations of CHX3 with A- anions afforded formation constants of both halogen- and hydrogen-bonded complexes between these species, which existed side-by-side in the acetonitrile solutions. The relative values of the formation constants were consistent with the magnitudes of the positive potentials on the surfaces of the halogen or hydrogen atoms if the effects of the polarization of the trihalomethanes due to the presence of the anions were taken into account.

Electron-transfer reactions of halogenated electrophiles: a different look into the nature of halogen bonding.

The rates of oxidation of ferrocene derivatives by brominated molecules R-Br (CBr3CN, CBr4, CBr3NO2, CBr3COCBr3, CBr3CONH2, CBr3F, and CBr3H) were consistent with the predictions of the outer-sphere dissociative electron-transfer theory. The similar redox-reactions of the R-Br electrophiles with the typical halogen-bond acceptors tetramethyl-p-phenylenediamine (TMPD) or iodide were much faster than calculated using the same model. The fast redox-processes in these systems were related to the involvement of the transient halogen-bonded [R-Br, TMPD] or [R-Br, I-] complexes in which barriers for electron transfer were lowered by the strong electronic coupling of reactants. The Mulliken-Hush treatment of the spectral and structural characteristics of the [R-Br, TMPD] or [R-Br, I-] complexes corroborated the values of coupling elements, Hab, of 0.2-0.5 eV implied by the kinetic data. The Natural Bond Orbital analysis of these complexes indicated a noticeable donor/acceptor charge transfer, Δq, of 0.03-0.09 e. The Hab and Δq values in the [R-Br, TMPD] and [R-Br, I-] complexes (which are similar to those in the traditional charge-transfer associates) indicate significant contribution of charge-transfer (weakly-covalent) interaction to halogen bonding. The decrease of the barrier for electron transfer between the halogen-bonded reactants demonstrated in the current work points out that halogen bonding should be taken into account in the mechanistic analysis of the reactions of halogenated species.

Mechanism and Thermodynamics of Reductive Cleavage of Carbon-Halogen Bonds in the Polybrominated Aliphatic Electrophiles.

Quantum-mechanical computations revealed that, despite the presence of electron-withdrawing and/or π-acceptor substituents, the lowest unoccupied molecular orbitals (LUMO) of the polybromosubstituted aliphatic molecules R-Br (R-Br = C3Br2F6, CBr3NO2, CBr3CN, CBr3CONH2, CBr3CO2H, CHBr3, CFBr3, CBr4, CBr3COCBr3) are delocalized mostly over their bromine-containing fragments. The singly occupied molecular orbitals in the corresponding vertically excited anion radicals (R-Br(•-))* are characterized by essentially the same shapes and show nodes in the middle of the C-Br bonds. An injection of an electron into the antibonding LUMO results in the barrierless dissociation of the anion-radical species and the concerted reductive cleavages of C-Br bonds leading to the formation of the loosely bonded {R(•)···Br(-)} associates. The interaction energies between the fragments of these ion-radical pairs vary from ∼10 to 20 kcal mol(-1) in the gas phase and from 1 to 3 kcal mol(-1) in acetonitrile. In accord with the concerted mechanism of reductive cleavage, all R-Br molecules showed completely irreversible reduction waves in the voltammograms in the whole range of the scan rates employed (from 0.05 to 5 V s(-1)). Also, the transfer coefficients α, established from the width of these waves and dependence of reduction peak potentials Ep on the scan rates, were significantly lower than 0.5. The standard reduction potentials of the R-Br electrophiles, E(o)R-Br/R·+X(-), and the corresponding R(•) radicals, E(o)R(•)/R(-), were calculated in acetonitrile using the appropriate thermodynamic cycles. In agreement with these calculations, which indicated that the R(•) radicals resulting from the reductive cleavage of the R-Br molecules are stronger oxidants than their parents, the reduction peaks' currents in cyclic voltammograms were consistent with the two-electron transfer processes.

From charge transfer to electron transfer in halogen-bonded complexes of electrophilic bromocarbons with halide anions.

Experimental and computational studies of the halogen-bonded complexes, [R-Br, X(-)], of bromosubstituted electrophiles, R-Br, and halide anions, X(-), revealed that decrease of a gap between the frontier orbitals of interacting species led to reduction of the energy of the optical charge-transfer transition and to increase in the ground-state charge transfer (X(-) → R-Br) in their associates. These variations were accompanied by weakening of the intramolecular, C-Br, and strengthening of the intermolecular, BrX(-), bonds. In the limit of the strongest electron donor-acceptor pairs, formation of the halogen-bonded complexes was followed by the oxidation of iodide to triiodide, which took place despite the fact that the I(-) → R-Br electron-transfer step was highly endergonic and the calculated outer-sphere rate constant was negligibly small. However, the calculated barrier for the inner-sphere electron transfer accompanied by the halogen transfer, R-BrI(-) → R˙Br-I(-)˙, was nearly 24 kcal mol(-1) lower as compared to that calculated for the outer-sphere process and the rate constant of such reaction was consistent with the experimental kinetics. A dramatic decrease of the electron-transfer barriers (leading to 18-orders of magnitude increase of the rate constant) was related to the strong electronic coupling of the donor and acceptor within the halogen-bonded precursor complex, as well as to the lower solvent reorganization energy and the successor-complex stabilization.

Interplay of Halogen and π-π Charge-Transfer Bondings in Intermolecular Associates of Bromo- or Iododinitrobenzene with Tetramethyl-p-phenylenediamine.

Two modes of intermolecular interactions (halogen and π-π charge-transfer bonding) between bromo- or iododinitrobenzene (XDNB) and tetramethyl-p-phenylenediamine (TMPD) are compared. X-ray crystallography revealed that TMPD·XDNB cocrystals comprise alternating donors/acceptors stacks formed by π-bonded (cofacial) TMPD and XDNB molecules. These structures also show two-point (C-X···O-N) halogen bonding between XDNB molecules resulting in formation of (XDNB)2 dimers. In solutions, XDNB and TMPD molecules formed 1:1 complexes showing strong absorption bands near 550 nm which followed the same Mulliken correlation as the associates of TMPD with the (halogen-free) nitro- and cyanobenzenes. In accord with the experimental data, density functional theory calculations with the M062X functional showed that TMPD·XDNB associates formed via π-π charge-transfer bonding are more stable (by 6-12 kcal/mol) than their halogen-bonded analogues. If XDNB is replaced with iodo- or bromoperfluorinated benzenes, or TMPD is replaced with pyridine, the energy gap between the π-π and halogen-bonded associates decreased. The analysis of the molecular-orbital interactions and surface electrostatic potentials of the interacting species indicated that charge-transfer contributions represent a critical component which determines variations of the strength of halogen bonding in these systems.

Halogen bond-assisted electron transfer reactions of aliphatic bromosubstituted electrophiles.

Isolation of pre-reactive complexes and analysis of kinetics of redox reactions of tetrabromomethane and tribromonitromethane demonstrated that halogen bonding results in significant lowering of the activation barriers for electron transfer, and that the rate constants of such (inner-sphere) processes can be evaluated from spectral, structural, and thermodynamic characteristics of the halogen-bonded associates.

Halogen bonding of electrophilic bromocarbons with pseudohalide anions.

UV-Vis measurements showed that the interaction of pseudohalide anions, A(-) (A(-) = N3(-), NCO(-), NCS(-)), with electrophilic bromocarbons, R-Br (R-Br = CBr4, CBr3NO2, CBr3CONH2, CBr3H, CBr3F, CBr3CN or C3Br2F6), in solution results in formation of [R-Br, A(-)] complexes. These associates are characterized by intense absorption bands in the 200-350 nm range showing distinct Mulliken correlation with the frontier (HOMO-LUMO) orbitals' separations of the interacting anion and the R-Br electrophile. X-ray crystallographic studies established the principal structural features of the halogen-bonded associates between bromocarbons and polydentate pseudohalide anions. Specifically, in the (Pr4N)NCO·CBr4, (Pr4N)N3·CBr4 and (Pr4N)NCO·CBr3NO2 co-crystals, bromine substituents of the electrophiles are halogen-bonded with the (C≡N or N=N) π-bonds of the cyanate or azide anions. Co-crystals of CBr4 with (Pr4N)NCS show two modes (C-Br···S-C and C-Br···N≡C) of halogen bonding, while tribromoacetamide molecules form C-Br···S-C halogen bonds and N-H···N≡C hydrogen bonds with thiocyanate anions. Structures and energetics of the halogen-bonded complexes resulted from the M06-2X/6-311+G(dp) computations of various R-Br-A(-) pairs were consistent with the experimental data. These computations revealed that the variations of the intramolecular (C-Br) and intermolecular (Br···A(-)) bond lengths are correlated with the A(-) → R-Br charge transfer determined from Natural Bond Orbital analysis. Also, the scrutiny of the structural data indicated that the locations of the intermolecular contacts in these associates are determined primarily by the frontier orbital shapes of the halogen-bonded species. Thus, spectral and structural data point out a significant role of molecular-orbital (charge-transfer) interactions in formation of halogen bonded complexes involving pseudohalides and bromocarbons.