New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands. Synthesis, characterization and stereoisomeric analysis

A new set of Ru-Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C3 symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2'-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)](+) have been prepared and thoroughly characterized. In the solid state, X-ray diffraction analysis techniques have been used. In solution, cyclic voltammetry (CV) and 1D and 2D NMR spectroscopy have been employed. DFT calculations have been also performed on these complexes and their achiral analogues previously reported in our group, to interpret and complement experimental results. Whereas isomerically pure complexes ([Ru(II)Cl(L2)(bpy)](BF4), 5 and [Ru(II)Cl(L2)(dppe)](BF4), 6) are obtained when starting from the highly symmetric [Ru(III)Cl3(L2)], 2, isomeric mixtures of cis, fac-[Ru(II)Cl(L1)(bpy)](BF4) (3b/3b'), trans,fac- (3a) and up/down,mer- (3c, 3d) isomers are formed when bpy is added to the less symmetric [Ru(III)Cl3(L1)], 1, in contrast to the case of the bulky dppe ligand that, upon coordination to 1, leads to the trans,fac-[Ru(II)Cl(L1)(dppe)](BF4) (4a) complex as a sole isomer due to steric factors.     

Biologically Inspired C−H and C=C Oxidations with Hydrogen Peroxide Catalyzed by Iron Coordination Complexes

The development of catalysts for the selective oxidation of readily available hydrocarbons or organic precursors into oxygenated products is a long‐standing goal in organic synthesis. In the last decade, some iron coordination complexes have shown the potential to fit this role. These catalysts can mimic the O?O activation mode of far more sophisticated iron oxygenase enzymes, generating powerful yet selective oxidants. In this review, we report state‐of‐the‐art C?H and C=C oxidations catalyzed by non‐heme iron complexes and H₂O₂ as the oxidant. Finally, we briefly describe some novel oxidative reactivity and the perspectives of this chemistry.     

Secondary kinetic isotope effect on the photoenolization of triplet o-methylanthrones. A microcanonical transition state theory calculation

The energy profile for the tautomerization reaction of 1,4-dimethylanthrone in the first triplet electronic state obtained through electronic calculations (B3LYP/ 6-31G(d)) is used to calculate the rate constants for the process at a wide range of energies using a modified RRKM microcanonical statistical formalism that takes into account tunneling. Through partial or total substitution of the hydrogen atoms of the methyl groups by deuterium atoms, it is possible to evaluate different primary and secondary kinetic isotope effects (KIE). These results can be compared with experimental data for these processes taking place in solid matrix at extremely low temperatures (4-50 K). Such a comparison allows us to conclude that the reaction is taking place at energies just slightly below (around 0.5 kcal/mol) the adiabatic potential energy barrier, a result that was previously found for other related molecules so that this mechanism may be extended to the photoenolization of other o-aryl methyl ketones. Analysis of the different factors contributing to the primary and secondary KIEs discloses that at energies not far below the adiabatic barrier, the tunneling effect is not the only factor that accounts for the large KIE but the differences in the energy level distribution upon isotopic substitution may be the predominant factor at a certain range of negative energies (this is especially so for the case of primary KIE). At positive energies (above the barrier) the levels factor is always the dominant factor in the total KIE.     

Properties of aromaticity indices based on the one-electron density matrix

Proper normalization of two previously published indices yields aromaticity measures that, when computed within the Hückel molecular orbital (HMO) approximation, closely match the topological resonance energies per pi electron of aromatic annulenes and their ions. The normalized indices, which quantify aromaticity of individual rings in polycyclic systems, are equally applicable to homocyclic and heterocyclic compounds and can be readily computed from 1-matrices calculated at any level of electronic structure theory. However, only the index ING, derived from the Giambiagi formula, produces proper ordering of aromaticities of heterocyclic compounds, provided it is calculated from all-electron wavefunctions in conjunction with the atoms in molecule (AIM) partitioning. Its values are shown to be strongly affected by electron correlation effects. Because of its apparent inability to distinguish between anti- and nonaromatic systems, ING should only be employed for aromatic species.     

Self-assembling of nanoscopic molecular rectangles, extended helicates and porous-like materials based on macrocyclic dicopper building blocks under fine supramolecular control

Upon reaction with a dicarboxylate linker, macrocyclic dicopper complexes encode for a selective supramolecular 2 + 2 self-assembly of nanoscopic rectangles, a new class of molecular helicates, and porous-like materials via fine structural control at three supramolecular levels.     

Table salt and other alkali metal chloride oligomers: structure, stability, and bonding

We have investigated table salt and other alkali metal chloride monomers, ClM, and (distorted) cubic tetramers, (ClM)(4), with M = Li, Na, K, and Rb, using density functional theory (DFT) at the BP86/TZ2P level. Our objectives are to determine how the structure and thermochemistry (e.g., Cl-M bond lengths and strengths, oligomerization energies, etc.) of alkali metal chlorides depend on the metal atom and to understand the emerging trends in terms of quantitative Kohn-Sham molecular orbital (KS-MO) theory. The analyses confirm the high polarity of the Cl-M bond (dipole moment, VDD, and Hirshfeld atomic charges). They also reveal that bond overlap derived stabilization (approximately -26, -20, and -8 kcal/mol), although clearly larger than in the corresponding F-M bonds, contributes relatively little to the (trend in) bond strengths (-105, -90, and -94 kcal/mol) along M = Li, Na, and K. Thus, the Cl-M bonding mechanism resembles more closely that of the even more ionic F-M bond than that of the more covalent C-M or H-M bonds. Tetramerization causes the Cl-M bond to expand, and it reduces its polarity.     

Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts

A novel family of chiral manganese complexes Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)] (MCP=N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)cyclohexane-trans-1,2-diamine), recently reported as a very efficient epoxidation catalyst in combination with peracetic acid. Pinene rings have been fused to the 4 and 5 positions of the two pyridine groups of the ligand, giving rise to complexes where the two labile binding sites of the manganese ion are confined in a better-defined chiral pocket than in the parent [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. Chirality in these complexes arises from the stereochemistry of the trans-diaminocyclohexane ring, from the pinene ring and also from the topological chirality adopted by the ligand upon binding to the manganese ion. While previous studies have demonstrated that small modifications in the structure of the MCP ligand result in a dramatic loss of efficiency, Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)) exhibit comparable catalytic activity to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. In addition, the complexes exhibit a remarkable stereoselectivity (up to 46% ee) in the epoxidation of selected substrates. The results reported in this work point towards modification of the 4 and 5 positions of the pyridine groups as a new strategy towards the design of stereoselective versions of this family of highly active and environmentally benign epoxidation catalysts.     

The Coulomb Hole of the Ne Atom

We analyze the Coulomb hole of Ne from highly-accurate CISD wave functions obtained from optimized even-tempered basis sets. Using a two-fold extrapolation procedure we obtain highly accurate results that recover 97 % of the correlation energy. We confirm the existence of a shoulder in the short-range region of the Coulomb hole of the Ne atom, which is due to an internal reorganization of the K-shell caused by electron correlation of the core electrons. The feature is very sensitive to the quality of the basis set in the core region and it is not exclusive to Ne, being also present in most of second-row atoms, thus confirming that it is due to K-shell correlation effects.     

Dötz Benzannulation Reactions: Heteroatom and Substituent Effects in Chromium Fischer Carbene Complexes

We have carried out a theoretical investigation of the Dötz reaction between acetylene and a series of chromium Fischer‐type carbenes [(CO)₅Cr?C(X)R] with different representative substituents (R=CH?CH₂, Ph) and heteroatom ligands (X=OH, NH₂, OCH₃, N(CH₃)₂) by using density functional theory with the B3LYP functional. We have studied the Dötz and chromahexatriene mechanisms of benzannulation and also the reaction mechanism leading to cyclopentannulation. For the benzannulation, it was found that the most likely mechanism in the case of vinylcarbenes is the chromahexatriene route, whereas for phenylcarbenes, the Dötz route via a ketene intermediate is clearly the most favorable. The reactions leading to the cyclopentannulated and benzannulated products are more exothermic with vinylcarbenes than with phenylcarbenes and also more exothermic with alkoxycarbenes than with aminocarbenes. The relative stability of the cyclopentannulated products as compared with the benzannulated products increases for bulkier X substituents and on going from alkoxy‐ to aminocarbenes. The kinetic data concurs with the experimental product distribution found for vinylcarbenes, by which mainly benzannulated products are obtained, and dimethylaminophenylcarbenes, which lead exclusively to cyclopentannulated adducts.