Bonds In Adducts Research Articles

Integrated Study on Methane Activation: Exploring Main Group Frustrated Lewis Pairs through Density Functional Theory, Machine Learning, and Machine-Learned Force Fields.

Frustrated Lewis Pairs (FLP) are an important advance in metal-free catalysis due to their ability to activate a variety of small molecules. Many studies have focused on a very limited sample of Lewis acids and bases. Herein, we disclose an automated exploration algorithm using density functional methods, artificial neural networks (ANNs), and a molecule builder that incentivizes the exploration of favorable FLP space for the activation of methane via two mechanisms: deprotonation and hydride abstraction. The exploration algorithm creates FLPs with different Lewis acids (LA), Lewis bases (LB), and their substituents (LA/LB), which proved successful in quickly converging in the favorable chemical space, suggesting chemically sound structures, and generating thousands of potential candidates for methane activating FLPs. By modeling thousands of reactions, an FLP database of methane activation was created, allowing one to data mine properties, e.g., adduct bond length, highest occupied molecular orbital-lowest-unoccupied molecular orbital (HOMO-LUMO) gap, global electrophilicity index, favored Lewis acids/bases/substituents, and substituent steric volume. These properties not only successfully narrow the FLP chemical space but also provide meaningful insight into the chemical nature of competent methane activators. The machine learning discovery strategy disclosed here is general enough to be applicable to many chemical optimization tasks. This study also investigates the efficacy of a Machine-Learned Force Field (MLFF) in predicting the formation energies of Frustrated Lewis Pairs (FLPs). Our model, exhibiting a test error of ±10 kcal/mol, highlighted impressive computational efficiency by enabling the calculation of all possible FLP permutations within our chemical space. The MLFF demonstrated proficiency in predicting energies, providing a significant acceleration compared to quantum mechanics methods. However, challenges emerged in accurately capturing forces, necessitating recourse to classical force fields for reliable structure relaxation. The present study sheds light on the MLFF's potential as a tool for rapid energy predictions, emphasizing the need for further refinement to enhance its accuracy, particularly in force predictions, to expand its utility in chemical simulations.

A new type of C+⋯Hδ-(C=) bond in adducts of vinyl carbocations with alkenes.

By X-ray diffraction analysis and IR spectroscopy, it was established here that vinyl carbocations C3H5+/C4H7+ with carborane counterion CHB11Cl11- form stable monosolvates C3H5+⋅C3H6/C4H7+⋅C4H8 with molecules of alkenes C3H6/C4H8. They contain molecular group =C+⋯Hδ--Cδ+= with a new type of bond formed by the H atom of the H-C= group of the alkene with the C atom of the C+=C group of the carbocation. The short C+----Cδ+ distance, equal to 2.44 Å, is typical of that of X----X in proton disolvates (L2H+) with an quasi-symmetrical X-H+⋯X moiety (where X = O or N) of basic molecule L. The nature of the discovered bond differs from that of the classic H-bond by an distribution of electron density: the electron-excessive Hδ- atom from the (=)C-H group of the alkene is attached to the C+ atom of the carbocation, on which the positive charge is predominantly concentrated. Therefore, it can be called an inverse hydrogen bond.

Dissociation energies of labile C—H bonds in adducts of thiyl radicals with quinoids

Dissociation energies of labile C—H bonds in adducts of thiyl radicals with quinoids

Competition of hydrogen, tetrel, and halogen bonds in COCl2-HOX (X=F, Cl, Br, I) complexes

The present study investigates the competition between hydrogen, halogen, and tetrel bonds from the interaction of COCl2 with HOX using quantum chemistry simulations at the MP2/aug-cc-pVTZ computational level, in which five configurations were optimized, including adducts I –V. Two hydrogen bonds, two halogen bonds, and two tetrel bonds were obtained for five forms of adducts. The compounds were investigated using spectroscopic, geometry, and energy properties. Adduct I complexes are more stable than others, and adduct V halogen bonded complexes are more stable than adduct II complexes. These results are in agreement with their NBO and AIM results. The stabilization energy of the XB complexes depends on the nature of both the Lewis acid and base. The stretching frequency of the O–H bond in adducts I, II, III, and IV displayed a redshift, and a blue shift was observed in adduct V. The results for the O-X bond showed a blue shift in adducts I and III and a red shift in adducts II, IV, and V. The nature and characteristics of three types of interactions are investigated via NBO analysis and atoms in molecules (AIM).

Leading Interaction Components in the Structure and Reactivity of Noble Gases Compounds.

The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological–theoretical approach. The identification of the leading interaction components in the noble gases adducts and their modeling allows the encompassing of the transitions from pure noncovalent to covalent bound aggregates and to rationalize the anomalous behavior (deviations from noncovalent type interaction) pointed out in peculiar cases. Selected adducts affected by a weak chemical bond, as those promoting the formation of the intermolecular halogen bond, are also properly rationalized. The behavior of noble gas atoms excited in their long-life metastable states, showing a strongly enhanced reactivity, has been also enclosed in the present investigation.

Xenon Trioxide Adducts of O‐Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3

Xenon trioxide (XeO3 ) forms adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone by coordination of the ligand oxygen atoms to the XeVI atom of XeO3 . The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction, and Raman spectroscopy. Unlike solid XeO3 , which detonates when mechanically or thermally shocked, solid (C5 H5 NO)3 (XeO3 )2 , [(C6 H5 )3 PO]2 XeO3 , and [(CH3 )2 SO]3 (XeO3 )2 are insensitive to mechanical shock. The [(CH3 )2 SO]3 (XeO3 )2 adduct slowly decomposes over several days to (CH3 )2 SO2 , Xe, and O2 . All three complexes undergo rapid deflagration when ignited by a flame. Both [(C6 H5 )3 PO]2 XeO3 and (C5 H5 NO)3 (XeO3 )2 are room-temperature stable and the [(CH3 )2 CO]3 XeO3 complex dissociates at room temperature to form a stable solution of XeO3 in acetone. The xenon coordination sphere of [(C6 H5 )3 PO]2 XeO3 , a distorted square-pyramid, provides the first example of a five-coordinate XeO3 complex with only two Xe- - -O adduct bonds. The xenon coordination spheres of the remaining adducts are distorted octahedra, comprised of three Xe- - -O secondary bonds that are approximately trans to the primary Xe-O bonds of XeO3 . Quantum-chemical calculations were used to assess the nature of the Xe- - -O adduct bonds, which are described as predominantly electrostatic bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the electrophilic xenon atoms.

Weak hydrogen bonds in adducts between freons: the rotational study of CH2F2–CH2ClF

The network of weak hydrogen bonds in CH2F2–CH2ClF suggests C–H⋯Cl–C to be preferred to C–H⋯F–C.

Competition between lone pair–π, halogen bond, and hydrogen bond in adducts of water with perhalogenated alkenes C2ClnF4−n (n = 0–4)

A thorough search of the potential energy surface is carried out for heterodimers of water with C2ClnF4−n. Three different types of interactions are observed. Structures dominated by a lone pair–π interaction have the highest binding energies, and are stabilized by charge transfer from O lone pairs of H2O to the CC π* antibonding orbital of the alkene. Halogen-bonded O⋯Cl complexes are slightly less strongly bound, followed by OH⋯X hydrogen bonds. The replacements of Cl by F atoms have only small effects upon binding energies. Inclusion of vibrational and entropic effects removes the clear energetic superiority of lp–π binding energies. When combined with the observation of several similar geometries for each particular heterodimer type, and a sensitivity to basis set, it would be quite difficult to predict with any degree of certainty the single most stable configuration, even with very high level calculations.

Theoretical and Structural Analysis of Long CC Bonds in the Adducts of Polycyanoethylene and Anthracene Derivatives and Their Connection to the Reversibility of Diels-Alder Reactions

X-ray structure determinations on four Diels-Alder adducts derived from the reactions of cyano- and ester-substituted alkenes with anthracene and 9,10-dimethylanthracene have shown the bonds formed in the adduction to be particularly long. Their lengths range from 1.58 to 1.62 Å, some of the longest known for Diels-Alder adducts. Formation of the four adducts is detectably reversible at ambient temperature and is associated with free energies of reaction ranging from -2.5 to -40.6 kJ mol(-1). The solution equilibria have been experimentally characterised by NMR spectroscopy. Density-functional-theory calculations at the MPW1K/6-31+G(d,p) level with PCM solvation agree with experiment with average errors of 6 kJ mol(-1) in free energies of reaction and structural agreement in adduct bond lengths of 0.013 Å. To understand more fully the cause of the reversibility and its relationship to the long adduct bond lengths, natural-bond-orbital (NBO) analysis was applied to quantify donor-acceptor interactions within the molecules. Both electron donation into the σ*-anti-bonding orbital of the adduct bond and electron withdrawal from the σ-bonding orbital are found to be responsible for this bond elongation.

The Weak Helps the Strong: Sigma-Holes and the Stability of MF4·Base Complexes

Bonding interactions between an electron-deficient region (a sigma-hole) on M and electron donors in MF4-Base complexes, where M = C, Si, Ge, Sn, and Pb, are examined and rationalized. These interactions are seen to transition from weak primarily noncovalent interactions for all bases when M = C to stronger primarily covalent bonds in adducts as the valence shell expands for the heavier M atoms. For M = Ge, Sn, and Pb, the complexes are particularly stable. The consistent axial preference in these systems is anticipated by previous studies and is readily explained from the vantage point of sigma-hole interactions. A series of bound complexes of common bases such as pyridine, tetrahydrofuran, and water are identified, some of which are even more stable than the SiF4·NH3 and SiF4·N(CH3)3 complexes that have already been identified experimentally. Sigma-hole bonding to di- and poly-substituted central atoms, perhaps on par with halogen bonding, is expected to become increasingly important as an ordering interaction in materials science and engineering. Group 14 compounds have distinct advantages in this respect.

Solventless Supramolecular Chemistry via Vapor Diffusion of Volatile Small Molecules upon a New Trinuclear Silver(I)-Nitrated Pyrazolate Macrometallocyclic Solid: An Experimental/Theoretical Investigation of the Dipole/Quadrupole Chemisorption Phenomena

A comparative study on the tendency of a new trinuclear silver(I) pyrazolate, namely, [N,N-(3,5-dinitropyrazolate)Ag]3 (1), and a similar compound known previously, [N,N-[3,5-bis(trifluoromethyl)pyrazolate]Ag]3 (2), to adsorb small volatile molecules was performed. It was found that 1 has a remarkable tendency to form adducts, at room temperature and atmospheric pressure, with acetone, acetylacetone, ammonia, pyridine, acetonitrile, triethylamine, dimethyl sulfide, and tetrahydrothiophene, while carbon monoxide, tetrahydrofuran, alcohols, and diethyl ether were not adsorbed. On the contrary, 2 did not undergo adsorption of any of the aforementioned volatile molecules. Adducts of 1 were characterized by elemental analysis, IR, thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area, and diffusion NMR measurements. The crystal structures of 1·2CH3CN and compound 3, derived from an attempt to crystallize the adduct of 1 with ammonia, were determined by single-crystal X-ray diffractometric studies. The former shows a sandwich structure with a 1:2 stoichiometric [Ag3]/[CH3CN] ratio in which one acetonitrile molecule points above and the other below the centroid of the Ag3N6 metallocycle. Compound 3 formed via rearrangement of the ammonia adduct to yield an anionic trinuclear silver(I) derivative with an additional bridging 3,5-dinitropyrazolate and having [Ag(NH3)2](+) as the counterion, [Ag(NH3)2][N,N-(3,5-dinitropyrazolate)4Ag3]. Irreversible sorption and/or decomposition upon vapor exposure are desirable advantages toward toxic gas filtration applications, including ammonia inhalation. TGA confirms the analytical data for all of the samples, showing weight loss for each adsorbed molecule at temperatures significantly higher than the corresponding boiling temperature, which suggests a chemical-bonding nature for adsorption as opposed to physisorption. BET surface measurements of the "naked" compound 1 excluded physical adsorption in its porous cavities. Density functional theory simulation results are also consistent with the chemisorption model, explain the experimental adsorption selectivity for 1, and attribute the lack of similar adsorption by 2 to significantly less polarizable electrostatic potential and also to strong argentophilic bonding whose energy is even higher than the quadrupole-dipole adduct bond energy upon proper selection of the density functional.

Hydroxyalkylation of Cyclic Imides with Oxiranes. Part II. The Mechanism of Reaction in Presence of Triethylamine

The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct of imide and triethylamine. The crucial bond in adduct has ionic character; in non-aqueous solvents it is present as ion pair, while in water the adduct dissociate and free ions are present. The adduct enables the proton transfer from imide to oxirane. The rate determining step is reaction of imide and this adduct. Different values of entropy of transition states obtained from thermodynamic calculations suggest slightly different structure of transition state of rate determining step.

ChemInform Abstract: Formation of a 1,3-Dipolar Nitro Addition Product from the Photochemical Reaction of 1,2-Dimethylnaphthalene and Tetranitromethane.

The photochemical reaction between tetranitromethane and 1,2-dimethylnaphthalene gives, among other adducts, a product of internal 1,3-dipolar cycloaddition of a nitro group from the trinitromethyl group across the 1,2-double bond of the primary adduct, 1,2-dimethyl-r-3-nitro-4-trinitrometnyl-3,4-dihydronaphthalene.

Syntheses and Multi-NMR Study offac- andmer-OsO3F2(NCCH3) and the X-ray Crystal Structure (n= 2) and Raman Spectrum (n= 0) offac-OsO3F2(NCCH3)·nCH3CN

Dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in CH(3)CN solvent at -40 degrees C followed by solvent removal under vacuum at -40 degrees C yielded fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN (n >/= 2). Continued pumping at -40 degrees C with removal of uncoordinated CH(3)CN yielded fac-OsO(3)F(2)(NCCH(3)). Both fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN and fac-OsO(3)F(2)(NCCH(3)) are yellow-brown solids and were characterized by low-temperature (-150 degrees C) Raman spectroscopy. The crystal structure (-173 degrees C) of fac-OsO(3)F(2)(NCCH(3)).2CH(3)CN consists of two co-crystallized CH(3)CN molecules and a pseudo-octahedral OsO(3)F(2).NCCH(3) molecule in which three oxygen atoms are in a facial arrangement and CH(3)CN is coordinated trans to an oxygen atom in an end-on fashion. The Os---N bond length (2.205(3) A) is among the shortest M---N adduct bonds observed for a d(0) transition metal oxide fluoride. The (19)F NMR spectrum of (OsO(3)F(2))(infinity) in CH(3)CN solvent (-40 degrees C) is a singlet (-99.6 ppm) corresponding to fac-OsO(3)F(2)(NCCH(3)). The (1)H, (15)N, (13)C, and (19)F NMR spectra of (15)N-enriched OsO(3)F(2)(NCCH(3)) were recorded in SO(2)ClF solvent (-84 degrees C). Nitrogen-15 enrichment resulted in splitting of the (19)F resonance of fac-OsO(3)F(2)((15)NCCH(3)) into a doublet ((2)J((15)N-(19)F), 21 Hz). In addition, a doublet of doublets ((2)J((19)F(ax)-(19)F(eq)), 134 Hz; (2)J((15)N-(19)F(eq)), 18 Hz) and a doublet ((2)J((19)F(ax)-(19)F(eq)), 134 Hz) were observed in the (19)F NMR spectrum that have been assigned to mer-OsO(3)F(2)((15)NCCH(3)); however, coupling of (15)N to the axial fluorine-on-osmium environment could not be resolved. The nitrogen atom of CH(3)CN is coordinated trans to a fluorine ligand in the mer-isomer. Quantum-chemical calculations at the SVWN and B3LYP levels of theory were used to calculate the energy-minimized gas-phase geometries, vibrational frequencies of fac- and mer-OsO(3)F(2)(NCCH(3)) and of CH(3)CN. The relative stabilities of the mer- and fac-isomers have been determined and are in accordance with the solution NMR assignments.

Methyl Gallate as the Framework for the Construction of Fluorous Building Blocks

Methyl gallate was used as the framework for the construction of the building blocks 3–5 with three fluorous ponytails. Fluorous gallate 3 was prepared from methyl gallate in three different pathways. The first is based on perfluorohexyl iodide addition to the corresponding allylderivative 1 and reduction of C-I bond in adduct 2; other ways are based on direct O-alkylation of methyl gallate by 3-(perfluorohexyl)propyl triflate and 3-(perfluorohexyl)propyl iodide, respectively. Reduction of polyfluoroalkylated gallate 3 provided benzyl alcohol 4, which can be easily converted to corresponding benzyl bromide 5.

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH(2)SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr(2) and its p-silylated derivative Me(3)Si--C(6)H(4)--BBr(2). The resulting compounds, R*--C(6)H(4)--B(Br)(CH(2)SMe) (R*=H: 2; R*=SiMe(3): 7) and PhB(CH(2)SMe)(2) (3), form cyclic dimers through B--S adduct bonds in solution and in the solid state. Compounds 2 and 3 have successfully been used for preparing the (N(2)S) scorpionate [PhBpz(2)(CH(2)SMe)](-) ([5](-)) (pz: pyrazol-1-yl) and the (NS(2)) scorpionate [PhBpz(CH(2)SMe)(2)](-), respectively. Compound 7 proved to be an excellent building block for the heteroditopic poly(pyrazol-1-yl)borate p-[pz(3)B--C(6)H(4)--Bpz(2)(CH(2)SMe)](2-) ([10](2-)) that mimics the two ligation sites of the copper enzymes peptidylglycine alpha-hydroxylating monooxygenase and dopamine beta-monooxygenase. Treatment of the monotopic tripod [5](-) with CuCl and CuBr(2) results in the formation of complexes K[Cu(5)(2)] and [Cu(5)(2)]. An X-ray crystallography study of K[Cu(5)(2)] revealed a tetrahedral (N(2)S(2)) coordination environment for the Cu(I) ion, whereas the Cu(II) ion of [Cu(5)(2)] possesses a square-pyramidal (N(4)S) ligand sphere (S-atom in the axial position). The remarkable redox properties of K[Cu(5)(2)] and [Cu(5)(2)] have been assessed by cyclic voltammetry and quantum chemical calculations. The reaction of K[Cu(5)(2)] with dry air leads to the Cu(II) species [Cu(5)(2)] and to a tetranuclear Cu(II) complex featuring [PhB(O)pz(2)](2-) ligands. Addition of CuCl to K(2)[10] gives the complex K(3)[Cu(10)(2)] containing two ligand molecules per Cu(I) center. The Cu(I) ion binds to both heteroscorpionate moieties and thereby establishes a coordination environment similar to that of the Cu(I) ion in K[Cu(5)(2)].

Efficient Synthesis of (±)-N-Boc-pregabalin via Hetero-Diels-Alder Addition of Methyl 3-Nitrosoacrylate to Ethyl Vinyl Ether

A new synthetic approach towards (±)-N-Boc-pregabalin is reported in this paper, which involves hetero-Diels-Alder addition of 3-nitrosoacrylate to ethyl vinyl ether and subsequent reduction of the C=N double bond of adduct, alteration of the ester functionality and reductive N-O bond scission followed by oxidation of the alcohol thus produced.

Experimental and Theoretical Studies of the Reaction of the OH Radical with Alkyl Sulfides: 1. Direct Observations of the Formation of the OH−DMS Adduct−Pressure Dependence of the Forward Rate of Addition and Development of a Predictive Expression at Low Temperature

A pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) system was employed to study the kinetics and mechanisms of reactions (1) OH + h6-DMS --> products and (2) OH + d6-DMS --> products. We report direct observations of the rate coefficients for the formation and dissociation of the h6-OHDMS and d6-OHDMS adducts over the pressure range 50-650 Torr and between 240 and 245 K, together with measurements of the oxygen dependence of the effective rate coefficients for reactions 1 and 2 under similar conditions. The effective rate coefficients increased as a function of O2 concentration reaching their limiting values in each case. The values of the adduct formation rate, obtained from the O2 dependencies, were in excellent agreement with values determined from direct observation of adduct equilibration in N2. OH regeneration is insignificant. The rate coefficients for the formation of the adduct isotopomers showed slight differences in their falloff behavior and do not approach the high-pressure limit in either case. The equilibrium constants obtained show no dependence on isotopomer and are in good agreement with previous work. A "second-law" analysis of the temperature dependence of the equilibrium constant gives an adduct bond strength (DeltaH degrees =-10.9 +/- 1.0 kcal mol(-1)), also in good agreement with previously reported values. Using the entropy calculated from the ab initio vibrational frequencies, we obtain a "third-law" value for the reaction enthalpy at 240 K, DeltaH(240K) degrees = -10.5 kcal mol(-1) in good agreement with the other approach. The rate coefficient for the reactions of the adducts with O2 was obtained from an analysis of the O2 dependence and was determined to be 6.3 +/- 1.2 x 10(-13) cm3 molecule(-1) s(-1), with no dependence on pressure or isotopomer. The pressure and temperature dependence for all of the elementary processes in the initial steps of the dimethylsulfide (DMS) oxidation mechanism have been characterized in the range 238-245 K, allowing the formulation of an expression which can be used to calculate the effective rate coefficient for reaction 1 at any pressure and oxygen concentration. The expression can calculate the effective rate coefficient for reaction 1 to +/- 40% over the range 220-260 K, with the largest errors at the extremes of this range. Gaussian 03 has been used to calculate the structure of the OH-DMS adduct and its deuterated isotopomer. We find similar bound structures for both isotopomers. The calculated enthalpies of formation of the adducts are lower than the experimentally determined values.

Kinetics, Mechanism, and Thermochemistry of the Gas Phase Reaction of Atomic Chlorine with Dimethyl Sulfoxide

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of chlorine atoms with dimethyl sulfoxide (CH3S(O)CH3; DMSO) as a function of temperature (270-571 K) and pressure (5-500 Torr) in nitrogen bath gas. At T = 296 K and P > or = 5 Torr, measured rate coefficients increase with increasing pressure. Combining our data with literature values for low-pressure rate coefficients (0.5-3 Torr He) leads to a rate coefficient for the pressure independent H-transfer channel of k1a = 1.45 x 10(-11) cm3 molecule(-1) s(-1) and the following falloff parameters for the pressure-dependent addition channel in N2 bath gas: k(1b,0) = 2.53 x 10(-28) cm6 molecule(-2) s(-1); k(1b,infinity) = 1.17 x 10(-10) cm3 molecule(-1) s(-1), F(c) = 0.503. At the 95% confidence level, both k1a and k1b(P) have estimated accuracies of +/-30%. At T > 430 K, where adduct decomposition is fast enough that only the H-transfer pathway is important, measured rate coefficients are independent of pressure (30-100 Torr N2) and increase with increasing temperature. The following Arrhenius expression adequately describes the temperature dependence of the rate coefficients measured at over the range 438-571 K: k1a = (4.6 +/- 0.4) x 10(-11) exp[-(472 +/- 40)/T) cm3 molecule(-1) s(-1) (uncertainties are 2sigma, precision only). When our data at T > 430 K are combined with values for k1a at temperatures of 273-335 K that are obtained by correcting reported low-pressure rate coefficients from discharge flow studies to remove the contribution from the pressure-dependent channel, the following modified Arrhenius expression best describes the derived temperature dependence: k1a = 1.34 x 10(-15)T(1.40) exp(+383/T) cm3 molecule(-1) s(-1) (273 K < or = T < or = 571 K). At temperatures around 330 K, reversible addition is observed, thus allowing equilibrium constants for Cl-DMSO formation and dissociation to be determined. A third-law analysis of the equilibrium data using structural information obtained from electronic structure calculations leads to the following thermochemical parameters for the association reaction: delta(r)H(o)298 = -72.8 +/- 2.9 kJ mol(-1), deltaH(o)0 = -71.5 +/- 3.3 kJ mol(-1), and delta(r)S(o)298 = -110.6 +/- 4.0 J K(-1) mol(-1). In conjunction with standard enthalpies of formation of Cl and DMSO taken from the literature, the above values for delta(r)H(o) lead to the following values for the standard enthalpy of formation of Cl-DMSO: delta(f)H(o)298 = -102.7 +/- 4.9 kJ mol(-1) and delta(r)H(o)0 = -84.4 +/- 5.8 kJ mol(-1). Uncertainties in the above thermochemical parameters represent estimated accuracy at the 95% confidence level. In agreement with one published theoretical study, electronic structure calculations using density functional theory and G3B3 theory reproduce the experimental adduct bond strength quite well.

Determination of Bond Dissociation Energies Using Electrospray Tandem Mass Spectrometry and a Derived Effective Reaction Path Length Approach

A new approach for calculating bond dissociation energies (BDEs) from ES-MS/MS measurements has been developed. The new method features a "derived effective reaction path length" that has been applied to measure BDEs of alkali metal (Li+) adducts and halide (Cl-) adducts of monoacylglycerol, 1,2-diacylglycerol, and 1,3-diacylglycerol lipids. Also studied were lithium-bound dimers of monoacylglycerols, 1,2-diacylglycerols, and 1,3-diacylglycerols. BDEs for the adducts and dimers of the lipids were derived from collision-induced dissociation experiments using a triple quadrupole mass spectrometer with electrospray as the ionization source. Mass spectral data were used to empirically derive a single-exponential growth equation that relates product cross section to collision energy. From these single-exponential equations, a general second-order polynomial was derived using a multivariate growth curve model that enables prediction of BDEs of unknown complexes. Mass spectral results were compared to computer-generated bond dissociation energies using Becke-style three-parameter density functional theory (B3LYP, employing the Lee-Yang-Parr correlation functional), with excellent agreement between experimental and theoretical energy values. The newly developed method is general in nature and can be used for the measurement of metal or halide ionic adduct bond dissociation energies and for the measurement of bond energies of noncovalent interactions such as dimer dissociation energies. The validity of the method has been rigorously established using a triple quadrupole, but it may also be applied to other mass spectrometers that allow user control of the collision cell potential.