Twin peaks: Matrix isolation studies of H2S·amine complexes shedding light on fundamental S-H⋯N bonding.

Noncovalent bonding between atmospheric molecules is central to the formation of aerosol particles and cloud condensation nuclei and, consequently, radiative forcing. While our understanding of O-H⋯B interactions is well developed, S-H⋯B hydrogen bonding has received far less attention. Sulfur- and nitrogen-containing molecules, particularly amines, play a significant role in atmospheric chemistry, yet S-H⋯N interactions are not well understood at a fundamental level. To help characterize these systems, H2S and methyl-, ethyl-, n-propyl-, dimethyl-, and trimethylamine (MA, EA, n-PA, DMA, and TMA) have been investigated using matrix isolation Fourier transform infrared spectroscopy and high-level theoretical methods. Experiments showed that H2S forms hydrogen bonded complexes with each of the amines, with bond strengths following the trend MA ≈ EA ≈ n-PA < TMA ≤ DMA, in line with past experimental work on H2SO4·amine complexes. However, the calculated results indicated that the trend should be MA < DMA < TMA, in line with past theoretical work on H2SO4·amine complexes. Evidence of strong Fermi resonances indicated that anharmonicity may play a critical role in the stabilization of each complex. The theoretical results were able to replicate experiment only after binding energies were recalculated to include the anharmonic effects. In the case of H2SO4·amine complexes, our results suggest that the discrepancy between theory and experiment could be reconciled, given an appropriate treatment of anharmonicity.

Closing the Shell: Gas-Phase Solvation of Halides by 1,3-Butadiene.

Gas-phase solvation of halides by 1,3-butadiene has been studied via a combination of photoelectron spectroscopy and density functional theory. Photoelectron spectra for X- ⋯(C4 H6 )n (X=Cl, Br, I where n=1-3, 1-3 and 1-7 respectively) are presented. For all complexes, the calculated structures indicate that butadiene is bound in a bidentate fashion through hydrogen-bonding, with the chloride complex showing the greatest degree of stabilisation of the internal C-C rotation of cis-butadiene. In both Cl- and Br- complexes, the first solvation shell is shown to be at least n = 4 ${n = 4}$ from the vertical detachment energies (VDEs), however for I- , increases in the VDE may suggest a metastable, partially filled, first solvation shell for n = 4 ${n = 4}$ and a complete shell at n = 6 ${n = 6}$ . These results have implications for gas-phase clustering in atmospheric and extraterrestrial environments.

Hydrogen Bonding versus Halogen Bonding: Spectroscopic Investigation of Gas-Phase Complexes Involving Bromide and Chloromethanes.

Hydrogen bonding and halogen bonding are important non-covalent interactions that are known to occur in large molecular systems, such as in proteins and crystal structures. Although these interactions are important on a large scale, studying hydrogen and halogen bonding in small, gas-phase chemical species allows for the binding strengths to be determined and compared at a fundamental level. In this study, anion photoelectron spectra are presented for the gas-phase complexes involving bromide and the four chloromethanes, CH3 Cl, CH2 Cl2 , CHCl3 , and CCl4 . The stabilisation energy and electron binding energy associated with each complex are determined experimentally, and the spectra are rationalised by high-level CCSD(T) calculations to determine the non-covalent interactions binding the complexes. These calculations involve nucleophilic bromide and electrophilic bromine interactions with chloromethanes, where the binding motifs, dissociation energies and vertical detachment energies are compared in terms of hydrogen bonding and halogen bonding.

Spectroscopic Study of the Br- +CH3 I→I- +CH3 Br SN 2 Reaction.

Mass spectrometry and anion photoelectron spectroscopy have been used to study the gas-phase S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction involving B r - ${{{\rm B}{\rm r}}^{-}}$ and C H 3 I ${{{\rm C}{\rm H}}_{3}{\rm I}}$ . The anion photoelectron spectra associated with the reaction intermediates of this S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction are presented. High-level CCSD(T) calculations have been utilised to investigate the reaction intermediates that may form as a result of the S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction along various different reaction pathways, including back-side attack and front-side attack. In addition, simulated vertical detachment energies of each reaction intermediate have been calculated to rationalise the photoelectron spectra.

Molecules of life: studying the interaction between water and phosphine in argon matrices.

The interaction between water and phosphine isolated in solid argon matrices has been investigated. Infrared spectra of matrices containing water and phosphine, as well as their deuterium and 18O isotopologues, revealed that a weak hydrogen bonded complex is formed, with an O-H⋯P bonding motif. This was supported by high level ab initio calculations, which predict a binding energy of only 5.1 kJ mol-1 (430 cm-1).

Halide-propene complexes: validated DSD-PBEP86-D3BJ calculations and photoelectron spectroscopy.

Anion photoelectron spectroscopy has been used to determine the electron binding energies of the X-⋯C3H6 (X = Cl, Br, I) complexes. To complement the experimental spectra the DSD-PBEP86-D3BJ functional has been employed, following comparison with previously calculated halide/halogen-molecule van der Waals complexes. To validate the functional, comparison between the complex geometries and vertical detachment energies with both experimental and CCSD(T)/CBS data for a suite of halide-molecule complexes is also made. PES spectra determine the electron binding energies as 3.89 eV and 4.00 eV, 3.59 eV and 4.01 eV, and 3.26 eV and 4.20 eV for transitions to perturbed 2P states of the chlorine, bromine and iodine complexes respectively. Two contributing structures resulting in the photoelectron spectrum are those where the halide is coordinated by two hydrogens, each from a terminal carbon in C3H6, and when bifurcating the CC bond. These complexes are distinct from the corresponding halide-ethene complexes and represent potential entry pathways to haloakyl radical formation in atmospheric and extraterrestrial environments.

A tale of two conformers: spectroscopic evidence for halide catalysed formic acid isomerisation.

Halide-formic acid complexes have been studied utilising a combined experimental and theoretical approach. Formic acid exists as two conformers, distinguished by the relative rotation about the C-OH bond. Computational investigation of the formic acid isomerisation reaction between the two conformers has revealed the ability of halide anions to catalyse the formation of, and preferentially stabilise, the higher energy conformer. Anion photoelectron spectroscopy has been used to study the halide-formic acid complexes, with the experimental vertical detachment energies compared with simulated photodetachment energies with respect to halide complexes with both formic acid conformers. The existence of experimental spectral features associated with halide complexes of the higher energy formic acid confomer confirms in situ generation, likely as a result of the halide mediated catalytic formation.

Photoelectron Spectroscopy and High-Level Ab Initio Calculations of the Iodide-Methylperoxy Radical Complex.

Anion photoelectron spectroscopy has been used to investigate the structure and dynamics of CH3OOI- van der Waals complexes. Peaks within the photoelectron spectrum are attributed to photodetachment to the perturbed 2P3/2 state of I···CH3OO (3.46 eV) and the two 2P states of bare iodine. A broad feature at 1.7-2.4 eV is attributed to detachment to the excited singlet states from two O2-···CH3I complexes. This represents the first anion photoelectron spectroscopy of a halide-bound methylperoxy radical species. Complex structures have been optimized using MP2/aug-cc-pVQZ with single-point energies at W1w theory for ground-state complexes and NEVPT2 for photodetachment to excited O2. Interactions are dominated by electrostatics, with the anion species interacting with the methyl pocket of the solvating molecule, suggesting conversion via an SN2 mechanism, and excess energy leading to complex dissociation within the timescale of mass spectrometry. The calculated W1w Gibbs energies suggest that while an electron transfer (ET) pathway to conversion is available, it is comparatively unfavored.

Photoelectron Spectroscopy and Structures of X- ⋠⋠⋠CH2 O (X=F, Cl, Br, I) Complexes.

A combined experimental and theoretical approach has been used to investigate X- ⋅⋅⋅CH2 O (X=F, Cl, Br, I) complexes in the gas phase. Photoelectron spectroscopy, in tandem with time-of-flight mass spectrometry, has been used to determine electron binding energies for the Cl- ⋅⋅⋅CH2 O, Br- ⋅⋅⋅CH2 O, and I- ⋅⋅⋅CH2 O species. Additionally, high-level CCSD(T) calculations found a C2v minimum for these three anion complexes, with predicted electron detachment energies in excellent agreement with the experimental photoelectron spectra. F- ⋅⋅⋅CH2 O was also studied theoretically, with a Cs hydrogen-bonded complex found to be the global minimum. Calculations extended to neutral X⋅⋅⋅CH2 O complexes, with the results of potential interest to atmospheric CH2 O chemistry.

Towards an Understanding of Halide Interactions with the Carbonyl-Containing Molecule CH3 CHO.

The anion photoelectron spectra of Cl- ⋅⋅⋅CD3 CDO, Cl- ⋅⋅⋅(CD3 CDO)2 , Br- ⋅⋅⋅CH3 CHO, and I- ⋅⋅⋅CH3 CHO are presented with electron stabilisation energies of 0.55, 0.93, 0.48, and 0.40 eV, respectively. Optimised geometries of the singly solvated species featured the halide appended to the CH3 CHO molecule in-line with the electropositive portion of the C=O bond and having binding energies between 45 and 52 kJ mol-1 . The doubly solvated Cl- ⋅⋅⋅(CH3 CHO)2 species features asymmetric solvation upon the addition of a second CH3 CHO molecule. Theoretical detachment energies were found to be in excellent agreement with experiment, with comparisons drawn between other halide complexes with simple carbonyl molecules.

Spectroscopic Investigation of Chalcogen Bonding: Halide-Carbon Disulfide Complexes.

A combined experimental and theoretical approach has been used to study intermolecular chalcogen bonding. Specifically, the chalcogen bonding occurring between halide anions and CS2 molecules has been investigated using both anion photoelectron spectroscopy and high-level CCSD(T) calculations. The relative strength of the chalcogen bond has been determined computationally using the complex dissociation energies as well as experimentally using the electron stabilisation energies. The anion complexes featured dissociation energies on the order of 47 kJ/mol to 37 kJ/mol, decreasing with increasing halide size. Additionally, the corresponding neutral complexes have been examined computationally, and show three loosely-bound structural motifs and a molecular radical.

Carbon-Rich Trinuclear Octamethylferrocenophanes.

Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1'-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl derivative (4a) by reaction with MeLi and AlCl3. The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6). Structure assignments are supported by X-ray crystallography and NMR spectroscopy, and mechanisms are proposed. Electrochemical behavior of the compounds was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of density functional theory calculations. The synthesized compounds and demonstrated transformations represent useful tools for preparation of materials for charge-transport studies in metal-molecule-metal junctions.

Matrix Isolation ESR and Theoretical Study of ZnN.

The Zn14N, 67Zn14N, Zn15N, and 67Zn15N radicals have been formed by the reaction of a plume of zinc metal produced with laser ablation and either ammonia vapor or nitrogen atoms isolated in an inert neon matrix at 4.3 K. The ground electronic state of ZnN was determined to be 4∑- using electron spin resonance spectroscopy. The following magnetic parameters were determined experimentally for ZnN: g⊥ = 1.9998(3), g∥ = 2.0018(3), | D| = 7268(8) MHz, A⊥(14N) = -17.9(20) MHz, A∥(14N) = 1.5(20) MHz, A⊥(15N) = 25.1(20) MHz, A∥(15N)= -2.0(20) MHz, A⊥(67Zn) = 156(3) MHz, and A∥(67Zn) = 168(12) MHz. The low-lying electronic states of ZnN were also investigated using the complete active space self-consistent field technique. By plotting the potential energy surface, theoretical parameters for the ground state with a configuration of 8σ29σ210σ14π2 were determined, including re = 2.079 Å and De = 1.0 kcal/mol.

A matrix isolation ESR investigation of Mg+-N2.

The adducts formed between 25Mg+ with 14N2 and 25Mg+ with 15N2 have been trapped in a solid neon matrix and studied with electron spin resonance (ESR) spectroscopy. These radical species were formed through the interaction of laser ablated magnesium and nitrogen gas. The Mg+-N2 radical species was found to have a ground electronic state of 2Σ+ in a linear configuration with discrete coupling to the proximate nitrogen resolved in the spectra. Fitting the ESR spectra allowed magnetic parameters to be determined as follows: g⊥ = 2.0012(5), g∥ = 2.0015(8), A⊥(1-14N) = 32(3) MHz, A∥(1-14N) = 34(5) MHz, A⊥(1-15N) = 45(4) MHz, A∥(1-15N) = 47(6) MHz, A⊥(25Mg) = -581(5) MHz, and A∥(25Mg) = -582(5) MHz, and estimates derived for A⊥(2-14N) = 1(2) MHz, A∥(2-14N) = 2(5) MHz, A⊥(2-15N) = 2(2) MHz, and A∥(2-15N) = 4(6) MHz. Ab initio calculations using the coupled-cluster single double triple methodology showed that the linear form was 59.7 kcal mol-1 more stable than the T-shaped form. The potential energy curve around the equilibrium geometry was explored using the complete active space self-consistent field approach, and Hartree-Fock singles and double configuration interaction and multireference singles and double configuration interaction calculations of the hyperfine coupling constants were undertaken, and reasonable agreement with the experiment was observed.

A matrix isolation ESR investigation of the MgCH radical.

The MgCH radical and its magnesium-25, carbon-13, and deuterated isotopologs have been isolated in low temperature neon matrices and examined by the matrix isolation electron spin resonance technique for the first time. The radicals were formed through the reactions of laser ablated natural abundance magnesium metal and magnesium-25 enriched magnesium metal with carbon-13 and deuterated isotopologs of acetone. The MgCH radical was shown to have a X4Σ- ground electronic state, and the magnetic parameters determined for this state were g⊥ = 2.001 81(45), g∥ = 2.0018(10), D = 4970(5) MHz, A⊥(13C) = 115(6) MHz, A∥(13C) = 65(15) MHz, A⊥(H) = 34(6) MHz, A∥(H) = 5(10) MHz, A⊥(D) = 5(3) MHz, A⊥(25Mg) = 82(5) MHz, and A∥(25Mg) = 85(10). Comparisons are made between the electronic structure of this radical and the MgCH3 and MgN radicals. Theoretical hyperfine parameters were also evaluated for the MgCH radical, and a potential energy surface for the low-lying electronic states was constructed using complete active space multiconfigurational self-consistent field theory. The leading configuration (96.6%) for the X4Σ- ground electronic state was shown to be 1σ22σ23σ21π44σ25σ26σ27σ12π12π1 with an Mg-C bond length of 2.041 Å for a fixed C-H bond length of 1.090 Å. The Mg-C bond dissociation energy (De) was 48.26 kcal/mol. The optimized geometry from a density functional theory calculation using the B3LYP functional gave a Mg-C bond length of 2.061 Å and a C-H bond length of 1.090 Å.

What Is the Structure of the Antitubercular Natural Product Eucapsitrione?

1,5,7-Trihydroxy-6H-indeno[1,2-b]anthracene-6,11,13-trione (1), proposed to be the antitubercular natural product eucapsitrione, has been synthesized in 43% overall yield and six steps, including a key Suzuki-Miyaura biaryl coupling and a directed remote metalation (DReM)-initiated cyclization. The physical and spectroscopic properties of 1 do not match the data reported for the natural product. At this time there is insufficient information available to enable a structure reassignment. During the optimization of the Suzuki-Miyaura coupling, an unprecedented biaryl coupling ortho to the borono group was observed. The scope of this unusual reaction has been investigated.

A matrix isolation ESR and theoretical study of MgN.

Matrix isolation experiments have been conducted on the Mg14N, 25Mg14N, Mg15N, and 25Mg15N radicals which were formed by the reaction of a plume of magnesium metal produced with laser ablation and either acetonitrile vapour or nitrogen atoms. The radicals were isolated in an inert neon matrix at 4.3 K and studied with electron spin resonance spectroscopy. The ground electronic state of MgN was determined to be 4Σ-. The following magnetic parameters were determined experimentally for MgN: g⊥ = 2.004 78 (2), g∥ = 2.001 72 (4), |D| = 9797 (6) MHz, A⊥(14N) = 19.7 (2) MHz, A∥ (14N) = -4.0 (3) MHz, A⊥(15N) = 27.5 (3) MHz, A∥ (15N) = -5.7 (3) MHz, A⊥ (25Mg) = -60.7 (5) MHz, and A∥(25Mg) = -65 (3) MHz. The low-lying electronic states of MgN were also investigated using the complete active space multiconfigurational self-consistent field technique. By plotting the potential energy surface, theoretical parameters for the ground state with a configuration of 5σ26σ27σ12π12π1 were able to be determined, including re = 2.090 Å and De = 11.28 kcal/mol.

Access to 1,2,3,4-Tetraoxygenated Benzenes via a Double Baeyer-Villiger Reaction of Quinizarin Dimethyl Ether: Application to the Synthesis of Bioactive Natural Products from Antrodia camphorata.

The first systematic investigation into the Baeyer-Villiger reaction of an anthraquinone is presented. The double Baeyer-Villiger reaction of quinizarin dimethyl ether is viable, directly providing the dibenzo[b,f][1,4]-dioxocin-6,11-dione ring-system, which is otherwise difficult to prepare. This methodology provides rapid access to 1,2,3,4-tetraoxygenated benzenes, and has been exploited by application to the total synthesis of a natural occurring benzodioxole and its biphenyl dimer, which both display noteworthy biological activity. Interestingly, the axially chiral biphenyl was found to be configurationally stable, but the resolved enantiomers exhibit no optical activity at the αD-line.

Influence of P-Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl-Substituted Phospholes.

2,5-Diferrocenyl-1-Ar-1H-phospholes 3 a-e (Ar=phenyl (a), ferrocenyl (b), mesityl (c), 2,4,6-triphenylphenyl (d), and 2,4,6-tri-tert-butylphenyl (e)) have been prepared by reactions of ArPH2 (1 a-e) with 1,4-diferrocenyl butadiyne. Compounds 3 b-e have been structurally characterized by single-crystal XRD analysis. Application of the sterically demanding 2,4,6-tri-tert-butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 (3 b), 295 (3 c), 340 (3 d), and 315 mV (3 e) in [NnBu4 ][B(C6 F5 )4]; these values indicate substantial thermodynamic stability of the mixed-valence radical cations. Monocationic [3 b](+)-[3 e](+) show intervalence charge-transfer absorptions between 4650 and 5050 cm(-1) of moderate intensity and half-height bandwidth. Compounds 3 c-e with bulky, electron-rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b.

Halide-Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations.

The gas phase anion photoelectron spectra are presented for the halide-nitrogen clusters X(-)···(N2)n, where X = Br and I and n ≤ 5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen-nitrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v "T-shaped" species and to a higher energy covalently bound "triangle" C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C∞v symmetry. The "T-shaped" geometry is a transition state linking equivalent C∞v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol(-1) and 7.0 kJ mol(-1) and 3.5 kJ mol(-1) and 5.0 kJ mol(-1) for the bromine and iodine species, respectively.