Non-classical structures of organic compounds are Non-classical structures of organic compounds are defined as molecules containing non-tetrahedral tetracoordinate defined as molecules containing non-tetrahedral tetracoordinate and/or hypercoordinate carbon atoms. The evolution of the views and/or hypercoordinate carbon atoms. The evolution of the views on this subject is considered and the accumulated theoretical and on this subject is considered and the accumulated theoretical and experimental data on the structures and dynamic transformations experimental data on the structures and dynamic transformations of non-classical organic compounds are systematised. It is shown of non-classical organic compounds are systematised. It is shown that computational analysis using the methods and the software that computational analysis using the methods and the software potential of modern quantum chemistry has now acquired high potential of modern quantum chemistry has now acquired high predictive capacity and is the most important source of data on the predictive capacity and is the most important source of data on the structures of non-classical compounds. The bibliography includes structures of non-classical compounds. The bibliography includes 227 references. 227 references.

Ab initio (RHF/LanL2DZ, MP2(fc)/LanL2DZ, MP2(fc)/6-31G**, and MP2(fc)/6-311++G**) calculations were performed for a series of β -chalcogenovinylaldehydes, 1,6-dioxa-6a-chalcogenopentalenes, and bimolecular complexes of formaldehyde with chalcogen hydrides and chlorides. The calculations reproduce well the existence and experimentally observed structural peculiarities of the intra- and intermolecular Ο - > chalcogen attractive interactions that stabilize the hypervalent T-shaped bond configuration at a chalcogen atom. These interactions increase in the order S, Se, Te and with the increasing electronegativity of a substituent attached to the chalcogen center. The ab initio calculations performed predict the existence of sufficiently stable bimolecular complexes H2CO . . .XR1R2 (X = S, Se, Te; R1, R2 = H, Cl) with a complexation energy comparable to the energy of a strong hydrogen bond.Key words: ab initio calculations, chalcogen-containing compounds, intramolecular coordination.

Strong attractive intramolecular X<--Y(S, NR') interactions of 1,5-type occurring between terminal electron-rich main-group 15-17 centers (X = pnictogen, chalcogen, or halogen) and carbonyl, thione, or imine groups (Y = O, S, NR') incorporated into the conjugated -X-CH=CH-CH=Y fragments result in significant stabilization of cis-s-cis structure of these molecules, which may be viewed as the five-membered pseudo-heterocycles with the hypervalent arrangements across the pnictogen, chalcogen, or halogen centers. In derivatives of beta-chalcovinylaldehydes and isoelectronic chloronium cations, one of two lone electron pairs at X = S, Se, Te, Cl+ possesses pure p character and is involved in conjugation with the pi-system of the rest of the molecule, which leads to an appreciable contribution of the aromatic stabilization of the 6 pi-electron ring closed by the X<--Y bond. The aromaticity of these structures evaluated through calculation of the homodesmotic stabilization energies (HSE) increases in parallel with an increase in the strength of the intramolecular coordination bonds, i.e., in the order X = S, Se, Te and with an increase in electronegativity of a substituent attached to the chalcogen atom. Clear manifestation of the aromatic character of the cis-s-cis isomers of beta-chalcovinylaldehydes, their imines, as well as congeneric thiones and chloronium cations comes from the theoretical and experimental evidence for the pronounced equalization (as compared with the open trans-s-trans isomers) of the CC bond lengths. The cooperative effects of the hypervalent bonding and aromaticity are most distinct in the bicyclic structures of 1,6,6a lambda 4-trichalcapentalenes, their 1,6-dioxa(aza) analogues, and 1,6-dioxa-3a-aza-6a lambda 4-pnictapentalenes, in which two conjugated -X-CH=CH-CH=Y fragments are fused together via the symmetric -Y-X-Y- triad. The assessments based on the HSE values indicate that the aromaticity of these 10 pi-electron compounds is estimated as about 30-50% of the aromatic character of the most aromatic bicyclic structure of naphthalene. As shown by extensive ab initio calculations, substantial hypervalent bonding effects also operate in the case of beta-pnictovinylaldehydes formed by second and lower row pnictogen atoms (X = P, As, Sb, Bi), providing for the enhanced stability of their cis-s-cis configuration with respect to the free-of-strain trans-s-trans structures. The bicyclic 1,6,6a lambda 5-dioxapnictapentalene structure is also the most energy favorable form of these compounds. However, by contrast with the chalcogen and halonium analogues, the pseudo-cyclic structure of beta-pnictovinylaldehydes and the bicyclic structure of 1,6,6a lambda 5-dioxapnictapentalenes are maintained through primarily the occurrence of the hypervalent bonding across the pnictogen centers, whereas pi-delocalization is not (or weakly) operative in these compounds. A possible explanation for this finding is the low p character of the single lone electron pair at the pnictogen and orientation of the axis of its...

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The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.