ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Ab initio studies of structural features not easily amenable to experiment : Part 40. Structural and conformational investigations of 2-butanone and 2-pentanone

The ab initio gradient refined 4-21G geometries of two conformations of 2-butanone and of six conformations of 2-pentanone are reported. The C---C---C=O torsional energies of both systems were determined with geometry optimization at each point and are compared with those previously calculated for some homologous aldehydes and carboxylic acids. In agreement with the structural trends known for C---H bonds in methyl groups adjacent to C=O, it is found that a C---C bond eclipsing an adjacent C=O bond is more stable and shorter than in a skew position (C---C---C= O = 120°). The sum total of the 4-21G results available for various systems may support the following general rule: in X--- C---C=O systems the C---X bond is relatively short when syn-coplanar with C==O (X---C---C= O = 0°), and relatively long when skew with C=O (X---C---C=O 120°).     

Ab initio studies of structural features not easily amenable to experiment. 38. Structural and conformational investigations of propanoic, 2-methylpropanoic,and butanoic acid

The structures and conformational energies of several conformations of propanoic acid, 2-methylpropanoic acid, and butanoic acid were determined by geometrically unconstrained ab initio gradient geometry refinement on the 4-21G level. The O?C? C? C torsional potentials of propanoic acid and butanoic acid are found to be practically identical. There are energy minima at 0° and 120°, and maxima in the 60° region and at 180°. In 2-methylpropanoic acid there are energy minima at H? C? C?O dihedral angles of 0° and 120°, and maxima at 60° and 180°. The exact positions of the maxima and minima of the H? C? C?O torsional potential of 2-methylpropanoic acid are found to be predictable from propanoic acid rotational-potential parameters. Some conformationally dependent, local geometry trends are discussed.     

Study of DyFe12−xMx compounds by57Fe and161Dy Mössbauer spectroscopy

DyFe_12?xM_x (M=Si,Ti,Cr) were studied with⁵⁷Fe and¹⁶¹Dy Mössbauer spectroscopy. The deduced coupling constants J_RFe of these compounds are about equal. It is found that Si is substituting one particular Fe-site, while Cr is substituting Fe randomly. In DyFe₁₀Si₂ two Fe-sites favour a c-axis anisotropy, while the third one favours the basal plane.     

Ab initio structural investigation of methyl and ethyl carbamate, and carbamyl choline

The molecular structures of four conformations of methylcarbamate, three forms of ethylcarbamate, four forms of ethylacetate, and of the trans-form of carbamylcholine, were determined by ab initio gradient geometry refinement on the 4-21G level, and the results are compared with the geometries of homologous systems. Significant changes in bond distances and angles are observed with torsional changes, but, barring long-range non-bonded interactions, they are to a large extent localized in that part of the system which is directly involved with the torsional transition; i.e., through-bond effects in a bond distance chain begin to be insignificant after a sequence of three bonds.     

Critical comparison of the ab initio and spectroscopic methyl-C?H bond length difference in acetyl compounds,CH3C(O) X

In order to provide additional data for the relative lengths of methyl-C? H bond distances in acetyl derivatives, which are difficult to determine accurately by the conventional tools of structural chemistry, the geometries of CH₃COH, CH₃COF, CH₃COCH₃, CH₃COOH, and CH₃CONH₂ were determined by ab initio SCF gradient optimization at the 5-31G** level and compared with previous 4-21G results. For acetaldehyde 6-311G⁴* calculations were also performed and the correlated methyl-C? H stretching potential energy functions were determined. It is found that the calculated differences between the in-plane and out-of-plane methyl-C? H bonds are practically independent of the computational scheme. The calculated results are in contrast to relative bond lengths obtained by some vibrational overtone spectroscopic studies, but are in perfect agreement with C? H bond length differences determined from isolated C? H stretching frequencies of partially deuterated compounds. The reliability of the latter, and other spectroscopic data concerning the assignment of the methyl-C? H vibrations are critically analyzed. On the basis of the available evidence we conclude: (1) the methyl groups of the CH₃C(?O)X systems here discussed contain one strong (in-plane) and two weak (out-of-plane) C? H bonds; (2) intensities of C? H local mode spectra do not provide a reliable basis for assignment to individual bonds.