Light‐driven metallo‐organic catalysis: Intramolecular photoelectron transfer in the heterodinuclear complex 1 facilitates the photocatalytic production of hydrogen and the selective hydrogenation of tolane to give cis‐stilbene. All three well‐coordinated parts of the supramolecular system are essential: the (tbbpy)2Ru fragment as a photoactive unit, the redox‐active bridging ligand as an electron relay and storage site, and the palladium as a catalytically active center.

A quantitative structure-reactivity relationship has been derived from the results of B3LYP/6-311+G calculations on the hydration of carbon dioxide by a series of zinc complexes designed to mimic carbonic anhydrase. The reaction mechanism found is general for all complexes investigated. The reaction exhibits a low (4-6 kcal/mol) activation energy and is exothermic by about 8 kcal/mol. The calculations suggest an equilibrium between Lipscomb and Lindskog intermediates. The effectiveness of the catalysis is a function of the nucleophilicity of the zinc-bound hydroxide and the nucleofugicity of the zinc-bound bicarbonate. Hydrogen bridging of the bicarbonate to NH moieties in the ligands also plays an important role.

The full reaction path for the conversion of carbon dioxide to hydrogencarbonate has been computed at the B3LYP/6-311+G** level, employing a [(NH(3))(3)Zn(OH)](+) model catalyst to mimic the active center of the enzyme. We paid special attention to the question of how the catalytic cycle might be closed by retrieval of the catalyst. The nucleophilic attack of the catalyst on CO(2) has a barrier of 5.7 kcal mol(-1) with inclusion of thermodynamic corrections and solvent effects and is probably the rate-determining step. This barrier corresponds well with prior experiments. The intermediate result is a Lindskog-type structure that prefers to stabilize itself via a rotation-like transition state to give a Lipscomb-type product, which is a monodentate hydrogencarbonate complex. By addition of a water molecule, a pentacoordinated adduct with pseudo-trigonal-bipyramidal geometry is formed. The water molecule occupies an equatorial position, whereas the hydrogencarbonate ion is axial. In this complex, proton transfer from the Zn-bound water molecule to the hydrogencarbonate ion is extremely facile (barrier 0.8 kcal mol(-1)), and yields the trans,trans-conformer of carbonic acid rather than hydrogencarbonate as the leaving group. The carbonic acid molecule is bound by a short O...H-O hydrogen bond to the catalyst [(NH(3))(3)Zn(OH)](+), in which the OH group is already replaced by that of an entering water molecule. After deprotonation of the carbonic acid through a proton relay to histidine 64, modeled here by ammonia, hydrogencarbonate might undergo an ion pair return to the catalyst prior to its final dissociation from the complex into the surrounding medium.

Lithium parameters have been optimized for Stewart's standard PM3 method. The average deviation of the heats of formation calculated for 18 reference compounds is 6.2 kcal/mol from the experimental or high-level ab initzo data; the average deviation with Li/MNDO is 18.9 kcal/mol. The average error in bond lengths is also reduced by a factor of two to three. Ionization potentials and dipole moments are reproduced with comparable accuracy than Li/MNDO. However, the mean deviation for the heats of formation of both methods increases when being applied to other systems, especially to small inorganic molecules. The applicability of the new parameter set is demonstrated further for various compounds not included in the reference set, for the calculation of the activation barriers of several lithiation reactions, as well as for the estimation of oligomerization energies of methyl lithium (including the tetramer). Li/PM3 gives reliable results even for large dimeric complexes, like [{4-(CH3CR)C&N}LiI2, containing TMEDA or THF as coligands and reproduces the haptotropic interaction between Li' and n-systems (e.g., in benzyl lithium) as well as the relative energies and structural features of compounds with "hypervalent" atoms (e.g., in lithiated sulfones). 0 1993 by John Wiley & Sons, Inc.