Donation Of Electron Density Research Articles

The trans effect in square‐planar platinum(II) complexes—A density functional study

The mechanism of substitution water exchange reactions in square planar trans-Pt[(NH(3))(2)T(H(2)O)](n+) complexes is studied (T = H(2)O, NH(3), OH(-), F(-), Cl(-), Br(-), H(2)S, CH(3)S(-), SCN(-), CN(-), PH(3), CO, CH(3)(-), H(-), C(2)H(4)). The trans effect is explained in terms of sigma-donation and pi-back-donation whose relative strengths are quantified by the changes of electron occupations of 5d platinum atomic orbitals. The sigma-donation strength is linearly correlated with the Pt-H(2)O (leaving ligand) bond length (trans influence). The kinetic trans effect strength correlates proportionally with the sigma-donation ability of the trans-ligand except the ligands with strong pi-back-donation ability that stabilizes transition state structure. The sigma-donation ability of the ligand is dependent on the sigma-donation strength of the ligand in the trans position. Therefore the trans effect caused by sigma-donation can be understood as a competition between the trans-ligands for the opportunity to donate electron density to the central Pt(II) atom. The influence of the trans effect on the reaction mechanism is also shown. For ligands with a very strong sigma-donation (e.g. CH(3)(-) and H(-)), the substitution proceeds by a dissociative interchange (I(d)) mechanism. Ligands with strong pi-back donation ability (e.g. C(2)H(4)) stabilize the pentacoordinated intermediate and the substitution proceeds by a two step associative mechanism. For ligands with weak sigma-donation and pi-back-donation abilities, the highest activation barriers have to be overcome and substitutions can be described by an associative interchange (I(a)) mechanism. The results are supported by the energy decomposition and the natural orbital analysis.

Density Functional Theory Study of the Adsorption of Formaldehyde on Pd4 and on Pd4/γ-Al2O3 Clusters

B3LYP/LANL2DZ and B3LYP/6-31G(d)-restricted and -unrestricted calculations are employed to calculate energies and adsorption forms of formaldehyde adsorbed on planar and on tetrahedral Pd4 clusters and on a Pd4 cluster supported on Al10O15. Formaldehyde adsorbs on planar Pd4 in the eta(2)(C,O)-di-sigma adsorption mode, while on tetrahedral Pd4, it adsorbs in the eta(2)(C,O)-pi adsorption mode. The adsorption energy on planar Pd4 is -21.4 kcal x mol(-1), whereas for the tetrahedral Pd4 cluster, the adsorption energy is -13.2 kcal x mol(-1). The latter value is close to experimental findings (-12 to -14 kcal x mol(-1)). Adsorption of formaldehyde on Pd4 supported on an Al10O15 cluster leads essentially to the same result as that found for adsorption on the tetrahedral Pd4 cluster. Charge density analysis for the interaction between formaldehyde and the Pd4 clusters indicates strong backdonation in the eta(2) adsorption mode, leading to positive charge on the Pd4 cluster. NBO analysis shows that the highly coordinated octahedral aluminum atoms of Al10O15 donate electron density to the supported Pd4 cluster, while tetrahedral aluminum atoms with lower coordination number have acidic nature and therefore act as electron acceptors.

Investigations of Acidity and Nucleophilicity of Diphenyldithiophosphinate Ligands Using Theory and Gas-Phase Dissociation Reactions

Diphenyldithiophosphinate (DTP) ligands modified with electron-withdrawing trifluoromethyl (TFM) substitutents are of high interest because they have demonstrated potential for exceptional separation of Am (3+) from lanthanide (3+) cations. Specifically, the bis( ortho-TFM) (L 1 (-)) and ( ortho-TFM)( meta-TFM) (L 2 (-)) derivatives have shown excellent separation selectivity, while the bis( meta-TFM) (L 3 (-)) and unmodified DTP (L u (-)) did not. Factors responsible for selective coordination have been investigated using density functional theory (DFT) calculations in concert with competitive dissociation reactions in the gas phase. To evaluate the role of (DTP + H) acidity, density functional calculations were used to predict p K a values of the free acids (HL n ), which followed the trend of HL 3 < HL 2 < HL 1 < HL u. The order of p K a for the TFM-modified (DTP+H) acids was opposite of what would be expected based on the e (-)-withdrawing effects of the TFM group, suggesting that secondary factors influence the p K a and nucleophilicity. The relative nucleophilicities of the DTP anions were evaluated by forming metal-mixed ligand complexes in a trapped ion mass spectrometer and then fragmenting them using competitive collision induced dissociation. On the basis of these experiments, the unmodified L u (-) anion was the strongest nucleophile. Comparing the TFM derivatives, the bis( ortho-TFM) derivative L 1 (-) was found to be the strongest nucleophile, while the bis( meta-TFM) L 3 (-) was the weakest, a trend consistent with the p K a calculations. DFT modeling of the Na (+) complexes suggested that the elevated cation affinity of the L 1 (-) and L 2 (-) anions was due to donation of electron density from fluorine atoms to the metal center, which was occurring in rotational conformers where the TFM moiety was proximate to the Na (+)-dithiophosphinate group. Competitive dissociation experiments were performed with the dithiophosphinate anions complexed with europium nitrate species; ionic dissociation of these complexes always generated the TFM-modified dithiophosphinate anions as the product ion, showing again that the unmodified L u (-) was the strongest nucleophile. The Eu(III) nitrate complexes also underwent redox elimination of radical ligands; the tendency of the ligands to undergo oxidation and be eliminated as neutral radicals followed the same trend as the nucleophilicities for Na (+), viz. L 3 (-) < L 2 (-) < L 1 (-) < L u (-).

Calcium Adsorption on MgO(100): Energetics, Structure, and Role of Defects

The adsorption of Ca on the MgO(100) surface at 300 K has been studied using microcalorimetry, in combination with LEED, AES, ISS, work function, sticking probability measurements, and density functional theory (DFT) calculations. The MgO(100) thin films (approximately 4 nm thick) were grown epitaxially on a 1 microm thick Mo(100) single-crystal. The sticking probability of Ca on MgO(100) at 300 K is unity. On the basis of AES and ISS measurements, it was determined that Ca grows mainly as 3D particles on the MgO(100) surface with a density of approximately 1 x 10(12) islands/cm2. Ca adsorbs initially at defect sites with a very high heat of adsorption (approximately 410 kJ/mol). DFT calculations attribute this high initial heat to Ca binding to kink sites (376 kJ/mol), step sites (205 kJ/mol), and lower concentrations of stronger binding sites. The heat of adsorption decreases rapidly with coverage, reaching a minimum of 162 kJ/mol at approximately 0.3 ML, where Ca is mainly adding to small 3D Ca clusters. Afterward, it increases to the value of bulk Ca heat of sublimation (178 kJ/mol) at approximately 1.2 ML, attributed to the increase in stability with increasing Ca particle size. A 1.0 eV decrease of the work function with Ca coverage from 0 to 0.3 ML indicates that Ca adsorbed at defects is cationic, in agreement with calculations showing that Ca donates electron density to the MgO. Light ion sputtering of the MgO(100) surface generates point defects, but these do not change the heat of adsorption versus coverage, implying that they do not nucleate Ca particles. Oxygen vacancies are a likely candidate; DFT calculations show that F and F+ center vacancies bind Ca more weakly than terrace sites. More extensive sputtering creates extended defects (such as steps and kinks) that adsorb Ca with heats of adsorption up to approximately 400 kJ/mol, similar to that at the intrinsic defect sites.

1,5-Anti Stereocontrol in the Boron-Mediated Aldol Reactions of β-Alkoxy Methyl Ketones: The Role of the Formyl Hydrogen Bond

The boron-mediated aldol reactions of certain types of beta-alkoxy methyl ketone show remarkably high levels of stereoinduction with achiral aldehydes, leading preferentially to 1,5-anti related stereocenters. Given the low levels of asymmetric induction usually observed in acetate aldol reactions, this is of great synthetic utility and has been used successfully in the total synthesis of a number of polyketide natural products. We have investigated the effects of the alkoxy protecting group (OMe, OPMB, PMP acetal, tetrahydropyran, and OTBS) present in the boron enolate on the level and sense of remote 1,5-stereoinduction, using density functional theory calculations (B3LYP/6-31G**). Our predictions of diastereoselectivity from comparison of the competing aldol transition structures are in excellent qualitative and quantitative agreement with experimentally reported values. We conclude that the boron aldol reactions of unsubstituted boron enolates proceed via boat-shaped transition structures in which a stabilizing formyl hydrogen bond exists between the alkoxy oxygen and the aldehyde proton. It is this interaction that leads to preferential formation of the 1,5-anti adduct, by minimizing steric interactions between the beta-alkyl group and one of the ligands on boron. In the case of silyl ethers, the preference for this internal hydrogen bond is not observed due to the size of the protecting group and the electron-poor oxygen atom that donates electron density into the adjacent silicon atom. We show that this stereochemical model is also applicable in rationalizing the 1,4-syn stereoselectivity of boron aldol reactions involving certain alpha-chiral methyl ketones. These detailed results may be summarized as a conformational diagram that can be used to predict the sense of stereoinduction.

An ab Initio and Density Functional Theory Study of the Structure and Bonding of Sulfur Ylides

Sulfur ylides are useful synthetic intermediates that are formed from the interaction between singlet carbenes and sulfur-containing molecules. Partial double-bond character frequently has been proposed as a key contributor to the stability of sulfur ylides. Calculations at the B3LYP, MP2, and CCSD(T) levels of theory employing various basis sets have been performed on the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) in order to investigate the structure and bonding of these systems. The following general properties of sulfur ylides were observed from the computational studies: C-S bond distances that are close in length to that of a typical C-S double bond, high charge transfer from the sulfide to the carbene, and large torsional rotation barriers. Analysis of the sulfur ylide charge distribution indicates that the unusually short C-S bond distance can be attributed in part to the electrostatic attraction between highly oppositely charged carbon and sulfur atoms. Furthermore, n --> sigma* stabilization arising from donation of electron density from the carbon lone pair orbital into S-H or S-C antibonding orbitals leads to larger than expected torsional barriers. Finally, natural resonance theory analysis indicates that the bond order of the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) is 1.4-1.5, intermediate between a single and double bond.

Methylrhenium Trioxide Revisited: Mechanisms for Nonredox Oxygen Insertion in an M−CH3 Bond

Methylrhenium trioxide (MTO) has the rare ability to stoichiometrically generate methanol at room temperature with an external oxidant (H2O2) under basic conditions. In order to use this transformation as a model for nonredox oxidative C-O coupling, the mechanisms have been elucidated using density functional theory (DFT). Our studies show several possible reaction pathways to form methanol, with the lowest net barrier (DeltaH++) being 23.3 kcal mol-1. The rate-determining step is a direct "Baeyer-Villiger" type concerted oxygen insertion into MTO, forming methoxyrhenium trioxide. The key to the low-energy transition state is the donation of electron density, first, from HOO(-) to the -CH3 group (making -CH3 more nucleophilic and HOO- more electrophilic) and, second, from the Re-C bond to both the forming Re-O and breaking O-O bonds, simultaneously (thus forming the Re-O bond as the Re-C bond is broken). In turn, the ability of MTO to undergo these transfers can be traced to the electrophilic nature of the metal center and to the absence of accessible d-orbitals. If accessible d-orbitals are present, they would most likely donate the required electron density instead of the M-CH3 moiety, and this bond would thus not be broken. It is possible that other metal centers with similar qualities, such as PtIV or IrV, could be competent for the same type of chemistry.

Metal–heptaiodide interactions in cyclomaltoheptaose (β-cyclodextrin) polyiodide complexes as detected via Raman spectroscopy

The Raman spectra of the cyclomaltoheptaose (β-cyclodextrin, β-CD) polyiodide complexes (β-CD) 2·NaI 7·12H 2O, (β-CD) 2·RbI 7·18H 2O, (β-CD) 2·SrI 7·17H 2O, (β-CD) 2·BiI 7·17H 2O and (β-CD) 2·VI 7·14H 2O (named β-M, M stands for the corresponding metal) are investigated in the temperature range of 30–140 °C. At room temperature all systems show an initial strong band at 178 cm −1 that reveals similar intramolecular distances of the disordered I 2 units (∼2.72 Å). During the heating process β-Na and β-Rb display a gradual shift of this band to the final single frequency of 166 cm −1. In the case of β-Sr and β-Bi, the band at 178 cm −1 is shifted to the final single frequencies of 170 and 172 cm −1, respectively. These band shifts imply a disorder–order transition of the I 2 units whose I–I distance becomes elongated via a symmetric charge-transfer interaction I 2 ← I 3 - → I 2 . The different final frequencies correspond to different bond lengthening of the disordered I 2 units during their transformation into well-ordered ones. In the Raman spectra of β-V, the initial band at 178 cm −1 is not shifted to a single band but to a double one of frequencies 173 and 165 cm −1, indicating a disorder–order transition of the I 2 molecules via a non-symmetric charge-transfer interaction I 2 ← I 3 - → I 2 . The above spectral data show that the ability of I 3 - to donate electron density to the attached I 2 units is determined by the relative position of the different metal ions and their ionic potential q/ r. The combination of the present results with those obtained from our previous investigations reveals that cations with an ionic potential that is lower than ∼1.50 (Cs +, Rb +, Na +, K + and Ba 2+) do not affect the Lewis base character of I 3 - . However, when the ionic potential of the cation is greater than ∼1.50 (Li +, Sr 2+, Cd 2+, Bi 3+ and V 3+), the M n+ ⋯ I 3 - interactions become significant. In the case of a face-on position of the metal (Sr 2+, Bi 3+) relative to I 3 - , the charge-transfer interaction is symmetric. On the contrary, when the metal (Li +, Cd 2+, V 3+) presents a side-on position relative to I 3 - , the charge-transfer interaction is non-symmetric.

Effects of Microsolvation on the Adenine−Uracil Base Pair and Its Radical Anion: Adenine−Uracil Mono- and Dihydrates

Microhydration effects upon the adenine-uracil (AU) base pair and its radical anion have been investigated by explicitly considering various structures of their mono- and dihydrates at the B3LYP/DZP++ level of theory. For the neutral AU base pair, 5 structures were found for the monohydrate and 14 structures for the dihydrate. In the lowest-energy structures of the neutral mono- and dihydrates, one and two water molecules bind to the AU base pair through a cyclic hydrogen bond via the N(9)-H and N(3) atoms of the adenine moiety, while the lowest-lying anionic mono- and dihydrates have a water molecule which is involved in noncyclic hydrogen bonding via the O4 atom of the uracil unit. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of the AU base pair are predicted to increase upon hydration. While the VDE and AEA of the unhydrated AU pair are 0.96 and 0.40 eV, respectively, the corresponding predictions for the lowest-lying anionic dihydrates are 1.36 and 0.75 eV, respectively. Because uracil has a greater electron affinity than adenine, an excess electron attached to the AU base pair occupies the pi* orbital of the uracil moiety. When the uracil moiety participates in hydrogen bonding as a hydrogen bond acceptor (e.g., the N(6)-H(6a)...O(4) hydrogen bond between the adenine and uracil bases and the O(w)-H(w)...N and O(w)-H(w)...O hydrogen bonds between the AU pair and the water molecules), the transfer of the negative charge density from the uracil moiety to either the adenine or water molecules efficiently stabilizes the system. In addition, anionic structures which have C-H...O(w) contacts are energetically more favorable than those with N-H...O(w) hydrogen bonds, because the C-H...O(w) contacts do not allow the unfavorable electron density donation from the water to the uracil moiety. This delocalization effect makes the energetic ordering for the anionic hydrates very different from that for the corresponding neutrals.

The reaction of ( p-FC 6H 4) 3PE (E = Se, S) with diiodine: The single crystal X-ray structures of ( p-FC 6H 4) 3PSe, ( p-FC 6H 4) 3PS, ( p-FC 6H 4) 3PSeI 2, and ( p-FC 6H 4) 3PSI 2

The reactions of the tris( p-fluorophenyl)phosphine chalcogenides ( p-FC 6H 4) 3PE (E = Se ( 1), E = S ( 2)) with diiodine have been performed. The products of these reactions are the 1:1 charge-transfer compounds ( p-FC 6H 4) 3PSeI 2 ( 3), and ( p-FC 6H 4) 3PSI 2 ( 4), which feature a linear E–I–I motif typical of these types of spoke or “molecular dart” adducts. The I–I bonds in 3 [I–I: 2.8888(12)/2.8950(11) Å] and 4 [I–I: 2.8042(17)/2.835(2) Å] are lengthened with respect to diiodine in the solid-state, which is consistent with donation of electron density from the chalcogen atom to the σ ∗ antibonding orbital of the diiodine molecule. The elongation of the I–I bonds is considerably lower in magnitude than is observed for many CT adducts of diiodine as a result of the relatively poor donating capability of the phosphine chalogenides 1 and 2. A comparison with the non-fluorinated analogues Ph 3PEI 2 (E = S and Se) shows that the fluorine atom has little apparent effect upon the strength of the CT adduct formed, and that the I–I bond lengths appear to be more influenced by steric effects. The P–E–I angles in 3 and 4 are more acute than in the non-fluorinated Ph 3PEI 2 analogues, and as a result the steric influence of the aryl rings may be more strongly felt. This steric effect may act in competition with the electronic effect which would otherwise result in a more pronounced shortening of the I–I bond, compared to analogous Ph 3PEI 2 (E = S and Se) systems, although the differences are relatively small, and may also be due to packing effects.

Short intermolecular N—Br...O=C contacts in 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione

In the title compound, C(5)H(6)Br(2)N(2)O(2), all atoms except for the methyl group lie on a mirror plane in the space group Pnma (No. 62). All bond lengths are normal and the five-membered ring is planar by symmetry. Two short intermolecular N-Br...O=C contacts [Br...O = 2.787 (2) and 2.8431 (19) Angstrom] are present, originating primarily from the O-atom lone pairs donating electron density to the antibonding orbitals of the N-Br bonds (delocalization energy transfers 3.27 and 2.11 kcal mol(-1)). The total stabilization energies of the Br...O interactions are 3.4828 and 2.3504 kcal mol(-1).

Syntheses, Characterization, and Dioxygen Reactivities of Cu(I) Complexes with cis,cis-1,3,5-Triaminocyclohexane Derivatives: A Cu(III)2O2 Intermediate Exhibiting Higher C−H Activation

Six Cu(I) complexes with cis,cis-1,3,5-triaminocyclohexane derivatives (R3CY, R = Et, iBu, and Bn), [Cu(MeCN)(Et3CY)]SbF6 (1), [Cu(MeCN)(iBu3CY)]SbF6 (2), [Cu(MeCN)(Bn3CY)]SbF6 (3), [Cu(CO)(Et3CY)]SbF6 (4), [Cu(CO)(iBu3CY)]SbF6 (5), and [Cu(CO)(Bn3CY)]SbF6 (6), were prepared to probe the ability of copper complexes to effectively catalyze oxygenation reactions. The complexes were characterized by elemental analysis, electrochemical and X-ray structure analyses, electronic absorption spectroscopy, IR spectroscopy, 1H NMR spectroscopy, and ESI mass spectrometry. The crystal structures of 1-3 and 6 and the CO stretching vibrations (nuCO) of 4-6 demonstrate that the ability of R3CY to donate electron density to the Cu(I) atom is stronger than that of the previously reported ligands, 1,4,7-triazacyclononane (R3TACN) and 1,4,7-triazacyclodecane (R3TACD). Reactions of complexes 1-3 with dioxygen in THF or CH2Cl2 at -105 to -80 degrees C yield bis(mu-oxo)dicopper(III) complexes 7-9 as intermediates as confirmed by electronic absorption spectroscopy and resonance Raman spectroscopy. The Cu-O stretching vibrations, nu(Cu-O) for 7 (16O2: 553, 581 cm-1and 18O2: 547 cm-1) and 8 (16O2: 571 cm-1 and 18O2: 544 cm-1), are observed in a lower energy region than previously reported for bis(micro-oxo) complexes. The decomposition rates of complexes 7-9 in THF at -90 degrees C are 2.78 x 10-4 for 7, 8.04 x 10-4 for 8, and 3.80 x 10-4 s-1 for 9. The decomposition rates of 7 and 8 in CH2Cl2 were 5.62 x 10-4 and 1.62 x 10-3 s-1, respectively, and the thermal stabilities of 7-9 in CH2Cl2 are lower than the values measured for the complexes in THF. The decomposition reactions obeyed first-order kinetics, and the H/D isotope experiments for 8 and 9 indicate that the N-dealkylation reaction is the rate-determining step in the decomposition processes. On the other hand, the decomposition reaction of 7 in THF results in the oxidation of THF (acting as an exogenous substrate) to give 2-hydroxy tetrahydrofuran and gamma-butyrolactone as oxidation products. Detailed investigation of the N-dealkylation reaction for 8 by kinetic experiments using N-H/D at -90 degrees C showed a kinetic isotope effect of 1.25, indicating that a weak electrostatic interaction between the N-H hydrogen and mu-oxo oxygen contributes to the major effect on the rate-determining step of N-dealkylation. X-ray crystal structures of the bis(micro-hydroxo)dicopper(II) complexes, [Cu2(OH)2(Et3CY)2](CF3SO3)2 (10), [Cu2(OH)2(iBu3CY)2](CF3SO3)2 (11), and [Cu2(OH)2(Bn3CY)2](ClO4)2 (12), which have independently been prepared as the final products of bis(micro-oxo)dicopper(III) intermediates, suggest that an effective interaction between N-H and mu-oxo in the Cu(III)2(micro-O)2 core may enhance the oxidation ability of the metal-oxo species.

Density functional study of the charge on Aun clusters (n=1–7) supported on a partially reduced rutile TiO2(110): Are all clusters negatively charged?

It is widely believed that small gold clusters supported on an oxide surface and adsorbed at the site of an oxygen vacancy are negatively charged. It has been suggested that this negative charge helps a gold cluster adsorb oxygen and weakens the O-O bond to make oxidation reactions more efficient. Given the fact that an oxygen vacancy is electron rich and that Au is a very electronegative element, the assumption that the Au cluster will take electron density from the vacancy is plausible. However, the density functional calculations presented here show that the situation is more complicated. The authors have used the Bader method to examine the charge redistribution when a Aun cluster (n=1-7) binds next to or at an oxygen vacancy on rutile TiO2(110). For the lowest energy isomers they find that Au1 and Au3 are negatively charged, Au5 and Au7 are positively charged, and Au2, Au4, and Au6 exchange practically no charge. The behavior of the Aun isomers having the second-lowest energy is also unexpected. Au2, Au3, Au5, and Au7 are negatively charged upon adsorption and very little charge is transferred when Au4 and Au6 are adsorbed. These observations can be explained in terms of the overlap between the frontier molecular orbitals of the gold cluster and the eigenstates of the support. Aun with even n becomes negatively charged when the lowest unoccupied molecular orbital has a lobe pointing in the direction of the oxygen vacancy or towards a fivefold coordinated Ti (5c-Ti) located in the surface layer; otherwise it stays neutral. Aun with odd n becomes negatively charged when the singly occupied molecular orbital has a lobe pointing in the direction of a 5c-Ti located at the vacancy site or in the surface layer, otherwise it donates electron density into the conduction band of rutile TiO2(110) becoming positively charged.

Characterization of the Methoxy Carbonyl Radical Formed via Photolysis of Methyl Chloroformate at 193.3 nm

This study investigates two features of interest in recent work on the photolytic production of the methoxy carbonyl radical and its subsequent unimolecular dissociation channels. Earlier studies used methyl chloroformate as a photolytic precursor for the CH3OCO, methoxy carbonyl (or methoxy formyl) radical, which is an intermediate in many reactions that are relevant to combustion and atmospheric chemistry. That work evidenced two competing C-Cl bond fission channels, tentatively assigning them as producing ground- and excited-state methoxy carbonyl radicals. In this study, we measure the photofragment angular distributions for each C-Cl bond fission channel and the spin-orbit state of the Cl atoms produced. The data shows bond fission leading to the production of ground-state methoxy carbonyl radicals with a high kinetic energy release and an angular distribution characterized by an anisotropy parameter, beta, of between 0.37 and 0.64. The bond fission that leads to the production of excited-state radicals, with a low kinetic energy release, has an angular distribution best described by a negative anisotropy parameter. The very different angular distributions suggest that two different excited states of methyl chloroformate lead to the formation of ground- and excited-state methoxy carbonyl products. Moreover, with these measurements we were able to refine the product branching fractions to 82% of the C-Cl bond fission resulting in ground-state radicals and 18% resulting in excited-state radicals. The maximum kinetic energy release of 12 kcal/mol measured for the channel producing excited-state radicals suggests that the adiabatic excitation energy of the radical is less than or equal to 55 kcal/mol, which is lower than the 67.8 kcal/mol calculated by UCCSD(T) methods in this study. The low-lying excited states of methylchloroformate are also considered here to understand the observed angular distributions. Finally, the mechanism for the unimolecular dissociation of the methoxy carbonyl radical to CH3 + CO2, which can occur through a transition state with either cis or, with a much higher barrier, trans geometry, was investigated with natural bond orbital computations. The results suggest donation of electron density from the nonbonding C radical orbital to the sigma* orbital of the breaking C-O bond accounts for the additional stability of the cis transition state.

Interactions between Single-Walled Carbon Nanotubes and Tetraphenyl Metalloporphyrins: Correlation between Spectroscopic and FET Measurements

The noncovalent functionalization, or complexation, of single-walled carbon nanotubes (SWNTs) with metallo-tetraphenyl porphyrins (M-TPPs) was monitored with UV−vis−NIR absorption spectroscopy and electroanalytical measurements using nanotube field-effect transistors (NTFETs). From combining both techniques, we have found that M-TTPs donate electron density exclusively into semiconducting SWNTs. Moreover, thin-film UV−vis−NIR absorption spectroscopy on SWNT/M−TPP complexes provides a well-resolved picture of the interaction between the SWNT S1 band and the electron-donating M−TPP. In total, the electron-donating properties of four different M-TPPs containing Mn(III), Co(II), Cu(II), and Zn(II) were compared, and the electronic affects of each are discussed.

Synthesis, Spectroscopic, and Structural Investigation of the Cyclic [N(PR2E)2]+ Cations (E = Se, Te; R = iPr, Ph): the Effect of Anion and R-Group Exchange

Two-electron oxidation of the [N(PiPr2E)2]- anion with iodine produces the cyclic [N(PiPr2E)2]+ (E =Se, Te) cations, which exhibit long E-E bonds in the iodide salts [N(PiPr2Se)2]I (4) and [N(PiPr2Te)2]I (5). The iodide salts 4 and 5 are converted to the ion-separated salts [N(PiPr2Se)2]SbF6 (6) and [N(PiPr2Te)2]SbF6 (7) upon treatment with AgSbF6. Compounds 4-7 were characterized in solution by multinuclear NMR, vibrational, and UV-visible spectroscopy supported by DFT calculations. A structural comparison of salts 4-7 and [N(PiPr2Te)2]Cl (8) confirms that the long E-E bonds in 4, 5, and 8 can be attributed primarily to the donation of electron density from a lone pair of the halide counterion into the E-E sigma* orbital (LUMO) of the cation. The phenyl derivative [N(PPh2Te)2]I (9) was prepared in a similar manner. However, the attempted synthesis of the selenium analogue, [N(PPh2Se)2]I, produced a 1:1 mixture of [N(PPh2Se)2(mu-Se)][I] (10) and [SeP(Ph2)N(Ph2)PI] (11). DFT calculations of the formation energies of 10 and 11 support the observed decomposition. Compound 10 is a centrosymmetric dimer in which two six-membered NP2Se3 rings are bridged by two I- anions. Compound 11 produces the nine-atom chain {[N(PPh2)2Se]2(mu-O)} (12) upon hydrolysis during crystallization. The reaction between [(TMEDA)NaN(PiPr2Se)2] and SeCl2 in a 1:1 molar ratio yields the related acyclic species [SeP(iPr2)N(iPr2)PCl] (13), which was characterized by multinuclear NMR spectroscopy and an X-ray structural determination.

Analysis of O2 Adsorption on Binary−Alloy Clusters of Gold: Energetics and Correlations

We report a B3LYP density-functional theory (DFT) analysis of O(2) adsorption on 27 Au(n)M(m) (m, n = 0-3 and m + n = 2 or 3; M = Cu, Ag, Pd, Pt, and Na) clusters. The LANL2DZ pseudopotential and corresponding double-zeta basis set was used for heavy atoms, while a 6-311+G(3df) basis set was used for Na and O. We employed basis-set superposition error (BSSE) corrections in the electronic adsorption energies at 0 K (deltaE(ads)) and also calculated adsorption thermodynamics at standard conditions (298.15 K and 1 atm), i.e., internal energy of adsorption (deltaU(ads)) and Gibbs free energy of adsorption (deltaG(ads)). Natural Bond Orbital (NBO) analysis showed that all the clusters donated electron density to adsorbed O(2) and we successfully predicted intuitive linear correlations between the NBO charge on adsorbed O(2), O-O bond length, and O-O stretching frequency. Although there was no clear trend in the O(2) binding energy (BE = -deltaE(ads)) on pure and alloy dimers, we found the following interesting trend for trimers: BE (MAu(2)) < BE (M(3)) < or = BE (M(2)Au). The alloy trimers containing only one Au atom are most reactive toward O(2) while those with two Au atoms are least reactive. These trends are discussed in the context of the ensemble effect and coulomb interactions. We found an approximate linear correlation between the O(2) BE and charge transfer to O(2) for all 27 clusters. The clusters having strongly electropositive Na atoms (e.g., Na(3) and Na(2)Au) donated almost one full electron to adsorbed O(2), and the BE is maximum on these clusters. Although O(2) dissociation is likely in such cases, we have restricted this study to trends in the adsorption of molecular O(2) only. We also found an approximate linear correlation between the charge transfer and BE versus energy difference between the bare-cluster HOMO and O(2) LUMOs, which we speculate to be a fundamental descriptor of the reactivity of small clusters toward O(2). Part of the scatter in these correlations is attributed to the differences in the O(2) binding orientations on different clusters (geometric effect). Relatively higher bare-cluster HOMO energy eases the charge transfer to adsorbed O(2) and enhances the reactivity toward O(2). The Frontier Orbital Picture (FOP) is not always useful in predicting the most favorable O(2) binding site on clusters. It successfully predicted the cluster-O(2) ground-state configurations for 10 clusters, but failed for the others. Finally, the energetics of fragmentation suggest that the bare and O(2)-covered clusters reported here are stable.

Activation energies of selenoxide elimination from Se-substituted selenocysteine

Transition states for selenoxide elimination have been determined for a series of Se-substituted selenocysteine (RSeCys) derivatives that have potential use in the prevention and treatment of cancer, either directly or in conjunction with cisplatin (to reduce its nephrotoxic effects). Reduced activation barriers vs R=Me and R=Ph are found when the alkyl chain length is increased or when activating groups are para to the selenide. Ortho substitution of Lewis bases stabilizes the transition state by directly donating electron density to the selenoxide. The results suggest that RSeCys derivatives incorporating the properties of glutathione peroxidase mimics will, upon oxidation, rapidly eliminate selenenic acid, a precursor to chemopreventative selenols.

Self-Doped Polyaniline/Poly(diallyldimethyl ammonium chloride) Complex: N-Type Doping with High Stability

The negatively charged oxygen donates an electron pair to the hydrogen, and the hydrogen attached to the nitrogen accordingly weakly bonds with oxygen. The nitrogen in the polyaniline backbone finally possesses extra negative charge due to the donation of electron density by the oxygen.

Vibrational Spectroscopy of Mass-Selected [UO2(ligand)n]2+Complexes in the Gas Phase: Comparison with Theory

The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm(-1) for [UO2(CH3COCH3)2]2+ and was systematically red shifted to 1000 and 988 cm(-1) by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from two to four and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes, although the uranyl asymmetric stretching frequencies were greater than those measured for acetone complexes having equivalent coordination, which is consistent with the fact that acetonitrile is a weaker nucleophile than is acetone. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3-6 cm(-1).