Activation of the C-I and C-OH bonds of 2-iodoethanol by gas phase silver cluster cations yields subvalent silver-iodide and -hydroxide cluster cations

The gas phase ion-molecule reactions of silver cluster cations (Ag(n)(+)) and silver hydride cluster cations (Ag(m)H(+)) with 2-iodoethanol have been examined using multistage mass spectrometry experiments in a quadrupole ion trap mass spectrometer. These clusters exhibit size selective reactivity: Ag(2)H(+), Ag(3)(+), and Ag(4)H(+) undergo sequential ligand addition only, while Ag(5)(+) and Ag(6)H(+) also promote both C-I and C-OH bond activation of 2-iodoethanol. Collision induced dissociation (CID) of Ag(5)HIO(+), the product of C-I and C-OH bond activation by Ag(5)(+), yielded Ag(4)OH(+), Ag(4)I(+) and Ag(3)(+), consistent with a structure containing AgI and AgOH moieties. Ag(6)H(+) promotes both C-I and C-OH bond activation of 2-iodoethanol to yield the metathesis product Ag(6)I(+) as well as Ag(6)H(2)IO(+). The metathesis product Ag(6)I(+) also promotes C-I and C-OH bond activation.DFT calculations were carried out to gain insights into the reaction of Ag(5)(+) with ICH(2)CH(2)OH by calculating possible structures and their energies for the following species: (i) initial adducts of Ag(5)(+) and ICH(2)CH(2)OH, (ii) the subsequent Ag(5)HIO(+) product, (iii) CID products of Ag(5)HIO(+). Potential adducts were probed by allowing ICH(2)CH(2)OH to bind in different ways (monodentate through I, monodentate through OH, bidentate) at different sites for two isomers of Ag(5)(+): the global minimum "bowtie" structure, 1, and the higher energy trigonal bipyramidal isomer, 2. The following structural trends emerged: (i) ICH(2)CH(2)OH binds in a monodentate fashion to the silver core with little distortion, (ii) ICH(2)CH(2)OH binds to 1 in a bidentate fashion with some distortion to the silver core, and (iii) ICH(2)CH(2)OH binds to 2 and results in a significant distortion or rearrangement of the silver core. The DFT calculated minimum energy structure of Ag(5)HIO(+) consists of an OH ligated to the face of a distorted trigonal bipyramid with I located at a vertex, while those for both Ag(4)X(+) (X = OH, I) involve AgX bound to a Ag(3)(+) core. The calculations also predict the following: (i) the ion-molecule reaction of Ag(5)(+) and ICH(2)CH(2)OH to yield Ag(5)HIO(+) is exothermic by 34.3 kcal mol(-1), consistent with the fact that this reaction readily occurs under the near thermal experimental conditions, (ii) the lowest energy products for fragmentation of Ag(5)HIO(+) arise from loss of AgI, consistent with this being the major pathway in the CID experiments.     

The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm

The photodissociation of allyl iodide (C3H5I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C3H3+. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*(2P(1/2)) is more important than previously suspected.     

两种烷基碘化物分子理论研究及其发射谱测量

利用密度泛函理论(DFT)的B3LYP方法, 对烷基碘化物分子C2H2F3I和n-C3H4F3I的C—I解离势能曲线进行了理论计算, 并采用B3LYP方法和MPn(n=2, 3, 4)方法精确计算了C—I键解离能. 解离能计算进行了零点振动能(ZPVE)校正, 并运用完全均衡校正法对基函数重叠误差(BSSE)进行校正. 利用微波放电激励方法, 对C2H2F3I和n-C3H4F3I的发射谱进行观测. 实验结果表明, 通过微波放电激励这两种分子, 均可产生1315 nm发射谱, 说明利用微波放电可使C2H2F3I和n-C3H4F3I分子的C—I键解离, 从而产生碘原子.     

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: Alkali metal cations and trimethyl phosphate

Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies (BDEs) of complexes of alkali metal cations to trimethyl phosphate, TMP. Endothermic loss of the intact TMP ligand is the only dissociation pathway observed for all complexes. Theoretical calculations at the B3LYP/6-31G* level of theory are used to determine the structures, vibrational frequencies, and rotational constants of neutral TMP and the M+(TMP) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level using the B3LYP/6-31G* optimized geometries. The agreement between theory and experiment is reasonably good for all complexes except Li+(TMP). The absolute M+-(TMP) BDEs are found to decrease monotonically as the size of the alkali metal cation increases. No activated dissociation was observed for alkali metal cation binding to TMP. The binding of alkali metal cations to TMP is compared with that to acetone and methanol.     

Theoretical Study of the Regioselectivity of the Interaction of 3-Methyl-4-pyrimidone and 1-Methyl-2-pyrimidone with Lewis Acids

A density functional theory (DFT) study is performed to determine the stability of the complexes formed between either the N or O site of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone molecules and different ligands. The studied ligands are boron and alkali Lewis acids, namely, B(CH(3))(3), HB(CH(3))(2), H(2)B(CH(3)), BH(3), H(2)BF, HBF(2), BF(3), Li(+), Na(+), and K(+). The acids are divided into two groups according to their hardness. The reactivity predictions, according to the molecular electrostatic potential (MEP) map and the natural bond orbital (NBO) analysis, are in agreement with the calculated relative stabilities. Our findings reveal a strong regioselectivity with borane and its derivatives preferring the nitrogen site in both pyrimidone isomers, while a preference for oxygen is observed for the alkali acids in the 3-methyl-4-pyrimidone molecule. The complexation of 1-methyl-2-pyrimidone with these hard alkali acids does not show any discrimination between the two sites due to the presence of a continuous delocalized density region between the nitrogen and the oxygen atoms. The preference of boron Lewis acids toward the N site is due to the stronger B-N bond as compared to the B-O bond. The influence of fluorine or methyl substitution on the boron atom is discussed through natural orbital analysis (NBO) concentrating on the overlap of the boron empty p-orbital with the F lone pairs and methyl hyperconjugation, respectively. The electrophilicity of the boron acids gives a good overall picture of the interaction capabilities with the Lewis base.     

Dissociation mechanisms of neutral methyl stearate and its hydrogen atom adduct formed from the respective positive ions by electron transfer

The mechanism of dissociation of neutral methyl stearate and its hydrogen atom adduct was investigated by charge inversion mass spectrometry using an alkali metal target. Migrations of functional groups in fatty acid ester ions are often observed during the dissociation of the cations in collisionally activated dissociation (CAD). In the charge inversion spectrum, the main dissociation channels of methyl stearate molecule are the loss of a CH3 radical or a H atom. To identify the source of the CH3 radical and the H atom, the charge inversion spectra of partially deuterated methyl stearate (C17H35COOCD3) were measured. The loss of CH3 occurred through elimination from the methoxy methyl group and that of H occurred through elimination from the hydrocarbon chain of the fatty acid group. In the protonated ester, a simultaneous loss of CH3 (from the methoxy methyl group) and a H atom or a H2 molecule was observed. The charge inversion process gave the dissociation fragments with almost no migration of atoms. Only a few peaks that were structure sensitive were observed in the higher mass region in the charge inversion spectra; these peaks were associated with dissociations of energy-selected neutral species, unlike the case of CAD spectra in which they result from dissociation of ions. Charge inversion mass spectrometry with alkali metal targets provided direct information on the dissociation mechanism of methyl stearate and its hydrogen atom adduct without any migration of functional groups.     

Competitive C-I versus C-CN reductive elimination from a Rh(III) complex. Selectivity is controlled by the solvent

The RhIII complex [(PNP)Rh(CN)(CH3)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH3)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.     

Synthesis and binding properties of calix[4]arenes with [2 + 2'] mixed ligating functional groups

A series of mixed [2 + 2'] p-tert-butylcalix[4]arene have been synthesised by selective 1,3-dialkylation of phenolic groups using various alkylating agents such as benzyl bromide, methyl iodide, ethyl bromoacetate, and 2-methoxyethyl tosylate. The extraction and complexation properties of the synthesized calixarenes towards alkali and alkaline earth metal cations have been investigated in acetonitrile by means of UV spectrophotometry and 1H NMR spectroscopy. The results show the formation of ML and/or ML2 species depending on the ligand and the cation. The enthalpies and entropies of complexation of alkali metal cations by a tetraglycol, diglycol-dibenzyl and diglycol-diester derivatives have been obtained from calorimetric measurements. The results revealed that the formation of ML species is controlled by enthalpy while the formation of ML2 from ML is entropy driven.     

硫醚中碳硫键室温选择性断裂反应的研究

本文研究了在四氟硼酸银存在下, 硫醚与碘甲烷室温下发生碳硫键选择性断裂反应。研究结果表明: 只有当二苄基硫醚的苯环对位连有强的供电子基团甲氧基时, 方可发生碳硫键的断裂。提出了一个离子型反应机理且碳硫键的断裂分三步完成。首先, 硫醚与甲基化试剂反应生成甲基锍盐; 继而, 此锍离子离解成由苄基碳正离子和硫醚组成的离子-偶极集合物; 最后, 甲基化试剂再进攻集合物中的硫醚, 从而导致碳硫键的断裂。     

Di-ionizable p-tert-butylcalix[4]arene-1,2-monothiacrown-3 ligands in the cone conformation: synthesis and metal ion extraction

A series of di-ionizable calix[4]arene-1,2-crown-3 compounds with a sulfur-containing unit bridging the proximate phenolic oxygens have been synthesized. The ionizable groups are oxyacetic acid and N-(X)sulfonyl oxyacetamide groups with X=methyl, phenyl, 4-nitrophenyl, and trifluoromethyl, which ‘tunes’ the acidity of the latter. The efficiency and selectivity of these novel ligands are assessed for competitive solvent extractions of alkali metal cations and of alkaline earth metal cations from aqueous solutions into chloroform. Also the efficiencies for single species extractions of Pb²⁺ and of Hg²⁺ are determined. The results are compared with those reported previously for related ligands in which only oxygen heteroatoms are present in the crown ether unit.     

Unparalleled,Enormous Metal–Carbon Bond Strength in PdCH2I+

Thermalized Pd⁺ cations activate methyl iodide by selective cleavage of a C? H bond under formation of PdCH₂I⁺ and an H-atom. This finding implies that the interaction energy between the metal cation and the CH₂I fragment and thus the metal–carbon bond strength exceeds 103 kcal/mol. Theory predicts that the energetically most favorable isomer of this ion exhibits the Pd⁺? CH₂? I structure, which is stabilized by an unprecedented bridging interaction between the two heavy atoms Pd and I.     

Femtosecond multichannel photodissociation dynamics of CH3I from the A band by velocity map imaging

The reaction times of several well-defined channels of the C-I bond rupture of methyl iodide from the A band, which involves nonadiabatic dynamics yielding ground state I(2P3/2) and spin-orbit excited I*(2P1/2) and ground and vibrationally excited CH3 fragments, have been measured by a combination of a femtosecond laser pump-probe scheme and velocity map imaging techniques using resonant detection of ground state CH3 fragments. The reaction times found for the different channels studied are directly related with the nonadiabatic nature of this multidimensional photodissociation reaction.     

Di-ionizable p-tert-butylcalix[4]arene-1,2-crown-3 ligands in cone and 1,2-alternate conformations: synthesis and metal ion extraction

Novel di-ionizable p-tert-butylcalix[4]arene-1,2-crown-3 ligands in cone and 1,2-alternate conformations were prepared as potential metal ion extractants. Selective bridging of proximal hydroxyl groups of the calix[4]arene platform by a crown-3 polyether unit was achieved under Mitsunobu reaction conditions. In addition to the carboxylic acid group, the acidity tunable N-(X)sulfonyl oxyacetamide functions [OCH(2)C(O)NHSO(2)X] with X group variation from methyl to phenyl to p-nitrophenyl to trifluomethyl were used as the proton-ionizable groups. Conformations and regioselectivities of the new ligands were established by (1)H and (13)C NMR spectroscopy. Competitive solvent extractions of alkali metal cations and of alkaline earth metal cations from aqueous solutions into chloroform were performed, as were single species extractions of lead(ii) and mercury(ii).     

Studies into the mechanism of CO-induced N2 cleavage promoted by an ansa-hafnocene complex and C-C bond formation from an observed intermediate

Carbonylation of the hafnocene dinitrogen complex, [Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-(t)Bu)Hf](2)(μ(2), η(2), η(2)-N(2)), yields the corresponding hafnocene oxamidide compound, arising from N(2) cleavage with concomitant C-C and C-N bond formation. Monitoring the addition of 4 atm of CO by NMR spectroscopy allowed observation of an intermediate hafnocene complex with terminal and bridging isocyanates and a terminal carbonyl. (13)C labeling studies revealed that the carbonyl is the most substitutionally labile ligand in the intermediate and that N-C bond formation in the bridging isocyanate is reversible. No exchange was observed with the terminal isocyanate. Kinetic data established that the conversion of the intermediate to the hafnocene oxamidide was not appreciably inhibited by carbon monoxide and support a pathway involving rate-determining C-C coupling of the isocyanate ligands. Addition of methyl iodide to the intermediate hafnocene resulted in additional carbon-carbon bond formation arising from CO homologation following nitrogen methylation. Similar reactivity with (t)BuNCO was observed where C-C coupling occurred upon cycloaddition of the heterocumulene. By contrast, treatment of the intermediate hafnocene with CO(2) resulted in formation of a μ-oxo hafnocene with two terminal isocyanate ligands.     

Identifying the presence of a disulfide linkage in peptides by the selective elimination of hydrogen disulfide from collisionally activated alkali and alkaline earth metal complexes

We report a new method for identifying disulfide linkages in peptides using mass spectrometry. This is accomplished by collisional activation of singly charged cationic alkali and alkaline earth metal complexes, which results in the highly selective elimination of hydrogen disulfide (H2S2). Complexes of peptides possessing disulfide bonds with sodium and alkaline earth metal are generated using electrospray ionization (ESI). Isolation followed by collision induced dissociation (CID) of singly charged peptide complexes results in selective elimination of H2S2 to leave newly formed dehydroalanine residues in the peptide. Further activation of the product yields sequence information in the region previously short circuited by the disulfide bond. For example, singly charged magnesium and calcium ion bound complexes of [Lys8]-vasopressin exhibit selective elimination of H2S2 via low-energy CID. Further isolation of the product followed by CID yields major b- and z-type fragments revealing the peptide sequence in the region between the newly formed dehydroalanine residues. Numerous model peptides provide mechanistic details for the selective elimination of H2S2. The process is initiated starting with a metal stabilized enolate anion at Cys, followed by cleavage of the S-C bond. An examination of the peptic digest of insulin provides an example of the application of the selective elimination of H2S2 for the identification of peptides with disulfide linkages. The energetics and mechanisms of H2S2 elimination from model compounds are investigated using density functional theory (DFT) calculations.     

Protonation Switching to the Least‐Basic Heteroatom of Carbamate through Cationic Hydrogen Bonding Promotes the Formation of Isocyanate Cations

We found that phenethylcarbamates that bear ortho‐salicylate as an ether group (carbamoyl salicylates) dramatically accelerate O?C bond dissociation in strong acid to facilitate generation of isocyanate cation (N‐protonated isocyanates), which undergo subsequent intramolecular aromatic electrophilic cyclization to give dihydroisoquinolones. To generate isocyanate cations from carbamates in acidic media as electrophiles for aromatic substitution, protonation at the ether oxygen, the least basic heteroatom, is essential to promote C?O bond cleavage. However, the carbonyl oxygen of carbamates, the most basic site, is protonated exclusively in strong acids. We found that the protonation site can be shifted to an alternative basic atom by linking methyl salicylate to the ether oxygen of carbamate. The methyl ester oxygen ortho to the phenolic (ether) oxygen of salicylate is as basic as the carbamate carbonyl oxygen, and we found that monoprotonation at the methyl ester oxygen in strong acid resulted in the formation of an intramolecular cationic hydrogen bond (>C?O⁺?H???O<) with the phenolic ether oxygen. This facilitates O?C bond dissociation of phenethylcarbamates, thereby promoting isocyanate cation formation. In contrast, superacid‐mediated diprotonation at the methyl ester oxygen of the salicylate and the carbonyl oxygen of the carbamate afforded a rather stable dication, which did not readily undergo C?O bond dissociation. This is an unprecedented and unknown case in which the monocation has greater reactivity than the dication.     

Methylation of 2-amino-δ2-thiazolin-4-one

It is shown that the nucleophilicity of the sodium salt of 2-amino-²-thiazolin-4-one with respect to dimethyl sulfate and methyl iodide is extremely low, regardless of the nature of the solvent. The anomalous (in the 4-thiazolidone series) behavior of this salt in methylation is explained by the low degree of heterolytic dissociation of the O-Na bond. The possible reasons for the inertness of the oxygen atom in the anions of 2-substituted 4-thiazolidones with respect to alkylating agents are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1046–1049, August, 1981.     

The potassium metal reduction of perylene in tetrahydrofuran: evidence for the perylene dianion

Reduction of perylene with potassium metal in tetrahydrofuran at room temperature yields the dianion, as determined by potassium metal uptake, by ¹H NMR of the anion solution, and by product analysis of a methyl iodide quench. There is no evidence for decomposition of the solvent, either to a butoxy fragment or to an ethyl-ene/enolate mixture, a result which is in contrast to previously reported work on the naphthalene/alkali metal/tetrahydrofuran systems.     

Photodissociation of CH3I: a full-dimensional (9D) quantum dynamics study

The photodissociation of methyl iodide in the A band is studied by full-dimensional (9D) wave packet dynamics calculations using the multiconfigurational time-dependent Hartree approach. The potential energy surfaces employed are based on the diabatic potentials of Xie et al. [J. Phys. Chem. A 2000, 104, 1009] and the vertical excitation energy is taken from recent ab initio calculations [Alekseyev et al. J. Chem. Phys.2007, 126, 234102]. The absorption spectrum calculated for exclusively parallel excitation agrees well with the experimental spectrum of the A band. The electronic population dynamics is found to be strongly dependent on the motion in the torsional coordinate related to the H(3)-C-I bend, which presumably is an artifact of the diabatic model employed. The calculated fully product state-selected partial spectra can be interpreted based on the reflection principle and suggests strong coupling between the C-I stretching and the H(3)-C-I bending motions during the dissociation process. The computed rotational and vibrational product distributions typically reproduce the trends seen in the experiment. In agreement with experiment, a small but significant excitation of the total symmetric stretching and the asymmetric bending modes of the methyl fragment can be seen. In contrast, the umbrella mode of the methyl is found to be too highly excited in the calculated distributions.     

Influence of d orbital occupation on the binding of metal ions to adenine

Threshold collision-induced dissociation of M(+)(adenine) with xenon is studied using guided ion beam mass spectrometry. M(+) includes all 10 first-row transition metal ions: Sc(+), Ti(+), V(+), Cr(+), Mn(+), Fe(+), Co(+), Ni(+), Cu(+), and Zn(+). For the systems involving the late metal ions, Cr(+) through Cu(+), the primary product corresponds to endothermic loss of the intact adenine molecule, whereas for Zn(+), this process occurs but to form Zn + adenine(+). For the complexes to the early metal ions, Sc(+), Ti(+), and V(+), intact ligand loss competes with endothermic elimination of purine and of HCN to form MNH(+) and M(+)(C(4)H(4)N(4)), respectively, as the primary ionic products. For Sc(+), loss of ammonia is also a prominent process at low energies. Several minor channels corresponding to formation of M(+)(C(x)H(x)N(x)), x = 1-3, are also observed for these three systems at elevated energies. The energy-dependent collision-induced dissociation cross sections for M(+)(adenine), where M(+) = V(+) through Zn(+), are modeled to yield thresholds that are directly related to 0 and 298 K bond dissociation energies for M(+)-adenine after accounting for the effects of multiple ion-molecule collisions, kinetic and internal energy distributions of the reactants, and dissociation lifetimes. The measured bond energies are compared to those previously studied for simple nitrogen donor ligands, NH(3) and pyrimidine, and to results for alkali metal cations bound to adenine. Trends in these results and theoretical calculations on Cu(+)(adenine) suggest distinct differences in the binding site propensities of adenine to the alkali vs transition metal ions, a consequence of s-dsigma hybridization on the latter.