Ring Strain Energy of Diheteropnictogeniranes El2 Pn (Pn=N, P, As, Sb)- Accurate versus Additive Approaches.

Accurate ring strain energy (RSE) values for sixty-six parent pnictogeniranes having two other identical p-block elements, El2 Pn, have been reported. A decrease in RSE was observed to correlate with an increase in the p character of the AO used in endocyclic bonds, which is particularly remarkable on descending the groups 15 and 16. The latter also parallels higher -NICS(1) values, which seems not to be related with an increase in aromaticity, as pointed out by other NICS-related criteria, but to atom-centred diatropic currents mostly arising from the presence of lone pairs. Only in case of pnictogenaditrieliranes Tr2 Pn (Tr=B, Al, Ga), the decrease of -NICS(1) is related to a lower Hückel-type 2π-electron aromaticity on descending group 13. The use of an additive methodology based on atom-strain contributions enables estimation of RSEs for a large majority of all possible three-membered rings containing group 13-16 elements with modest accuracy (RMSE=4.371 kcal/mol), that could be remarkably improved by using bond-strain contributions (RMSE=1.183 kcal/mol) instead.

Ring Strain Energies of Three-Membered Homoatomic Inorganic Rings El3 and Diheterotetreliranes El2Tt (Tt = C, Si, Ge): Accurate versus Additive Approaches.

Accurate ring strain energies (RSEs) for three-membered symmetric inorganic rings El3 and organic dihetero-monocycles El2C and their silicon El2Si and germanium El2Ge analogues have been computed for group 14-16 "El" heteroatoms using appropriate homodesmotic reactions and calculated at the DLPNO-CCSD-(T)/def2-TZVPP//B3LYP-D4/def2-TZVP(ecp) level. Rings containing triels and Sn/Pb heteroatoms are studied as exceptions to the RSE calculation as they either do not constitute genuine rings or cannot use the general homodesmotic reaction scheme due to uncompensated interactions. Some remarkable concepts already related to the RSE such as aromaticity or strain relaxation by increasing the s-character in the lone pair (LP) of the group 15-16 elements are analyzed extensively. An appealing alternative procedure for the rapid estimation of RSEs using additive rules, based on contributions of ring atoms or endocyclic bonds, is disclosed.

Accurate Ring Strain Energies of Unsaturated Three-Membered Heterocycles with One Group 13-16 Element.

High-quality ring strain energy (RSE) data for 1H-unsaturated (CH)2X parent rings, where X is a group 13-16 element, are reported in addition to the 2H-isomers of the pnictogenirene rings. RSE data are obtained from appropriate homosdesmotic reactions and calculated at the DLPNO-CCSD(T)/def2-TZVPP//B3LYP-D3/def2-TZVP(ecp) level. 1H-Tallirene and 1H-plumbirene have unique donor-acceptor structures between an acetylene π(CC) orbital and an empty p orbital of a metallylene subunit (a Dewar-Chatt-Duncanson description) and therefore cannot be described as proper rings but as pseudocyclic structures. Also, 1H-indirene and 1H-oxirene lack ring critical points and constitute borderline cases of pseudorings. 1H-Unsaturated rings exhibit enhanced RSE compared to their saturated homologues. The mechanism of ring strain relaxation by increasing the s character in the lone pair (LP) of group 15-16 elements is remarkable and increases on descending the groups. Furthermore, RSE is affected by the aromatic character of group 13 rings and certain aromatic or antiaromatic character in group 14 or 15-16 rings, respectively, which tend to vanish on descending the group as shown by NICS(1) values. 2H-Unsaturated rings were found only for group 15 elements (although only 2H-azirine shows a proper cyclic structure) and displayed lower RSE (higher stability) than the corresponding 1H-isomers.

Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play.

Several phosphaquinodimethanes and their M(CO)5 complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH2 substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.

Accurate Ring Strain Energy Calculations on Saturated Three-Membered Heterocycles with One Group 13-16 Element.

Accurate ring strain energy (RSE) data for parent (CH2)2X rings are reported, where X are group 13-16 elements (El) in their lowest oxidation state, from the second to the sixth row, with their covalence completed by bonds to H. They are obtained from appropriate homodesmotic and hyper-homodesmotic reactions at different levels up to the CCSD(T) level, thus providing a benchmark of high-quality reference RSE values, as well as acceptably accurate faster lower-level options. Derivatives of indium, thallium, and lead cannot be properly described by a three-member ring connectivity, because they display a unique donor-acceptor structure from an ethylene π(C═C) orbital to an empty p orbital of a metallylene subunit. The RSE of groups 13 and 14 heterocycles increases on descending in the group (except for Ga and Ge), while it decreases for groups 15 and 16. The latter is presumably due to a strain-releasing mechanism favored by the increase of p-character at the sp3-type atomic orbital used by El in the endocyclic El-C bonds, %p(El)El-C, originated by the tendency of the El lone pairs in groups 15-16 to increase their s-character. This strain-releasing mechanism does not exist in heavier tetrels, which keep almost unchanged the p-character in the endocyclic bonds at El, whereas for triels the p-character is still lower owing to their sp2-like hybridization. Remarkable linear correlations were found between the RSE and either the above-mentioned %p(El)El-C, the distal C-C bond distance or the relaxed force constants for the endocyclic bond angles.

1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene.

1,2-Insertion reactions of alkynes into the Ge-C bonds in dibromodigermenes afford stable crystalline bromovinylgermylenes. In contrast to previously reported Lewis-base-supported vinylgermylenes, the bromovinylgermylene obtained from reaction of the bromogermylene with 3-hexyne via such an 1,2-insertion is a donor-free monomer. A feasible reaction mechanism, proposed on the basis of the observed experimental results in combination with theoretical calculations, suggests that the [1+2]-cycloadduct and the insertion product are the kinetic and thermodynamic product, respectively.

Computed tomographic diagnosis of unilateral cavernous sinus syndrome caused by a chondrosarcoma in a dog: a case report.

An eight-year old Rottweiler dog was presented with signs of enophthalmia, ptosis, anisocoria and mydriasis of the right eye, which showed visual disturbance, reduced or absent reflexes, and ophthalmoplegia. Consensual pupillary light reflex was also absent in the left eye. These neurological deficits were compatible with cavernous sinus syndrome. Computed tomography images of the cavernous sinus and the optical fissure revealed a mildly calcified mass arising from the right presphenoid bone extending further caudally into the orbital foramina. This extension of the mass affected the normal function of several cranial nerves. The dog was euthanased within one year of the initial presentation following development of forebrain signs. A chondrosarcoma was diagnosed histologically after necropsy.