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.

A series of bi[n]prismanes and tri[n]prismanes (n = 3-6) containing n and 2n, respectively, tetracoordinated carbon centers with nonclassical bisphenoidal (half-planar) configuration has been designed computationally.

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Using previously proposed C(BH)2(CH)2 (16, 17) and C(CH)2B2 (22) systems with a central planar tetracoordinate carbon (ptC) atom linking two three-membered rings as building blocks, a series of stable structures containing two and three ptC centers within a molecule have been designed and computationally studied with the DFT (B3LYP/6-311+G) method. Inclusion of a carbon atom ligated with pi-accepting and sigma-donating boron centers into at least one aromatic ring is critical for stabilization of a planar structure. A square pyramidal configuration at tetracoordinate carbon may be achieved in appropriately strained molecules such as [3.3.3.3]tetraborafenestrane 45 and others by surrounding the carbon with boron-centered ligands.