We present a theoretical study on possible models of catalytic active species corresponding to Ti–chloride species adsorbed at the corners of MgCl2 crystallites. First we focused our efforts on the interaction between prototypes of three industrially relevant Lewis bases used as internal donors (1,3-diethers, alkoxysilanes and succinates) and MgCl2 units at the corner of a MgCl2 crystallite. Our calculations show that the energetic cost to extract MgCl2 units at the corner of (104) edged MgCl2 crystallites is not prohibitive, and that Lewis bases added during catalyst preparation make this process easier. After removal of one MgCl2 unit, a short (110) stretch joining the (104) edges is formed. Adsorption of TiCl4 on the generated vacancy originates a Ti-active species. In the second part of this manuscript, we report on the stereo- and regioselective behavior of this model of active species in the absence as well as in the presence of the three Lewis bases indicated above. Surface reconstruction due to the additional adsorption of an extra MgCl2 layer is also considered. We show that, according to experimental data, Lewis bases coordinated in the proximity of the active Ti center confer a remarkable stereoselectivity. Moreover, surface reconstruction as well as donor coordination would improve regioselectivity by disfavoring secondary propene insertion. While still models of possible active species, our results indicate that defects, corners and surface reconstruction should be considered as possible anchoring sites for the catalytically active Ti-species.
In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE(1/2) potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C(ipso) of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C(ipso) atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group.
Non-natural (synthetic) nucleobases, including 7-ethynyl- and 7-triazolyl-8-aza-7-deazaadenine, have been introduced in RNA molecules for targeted applications, and have been characterized experimentally. However, no theoretical characterization of the impact of these modifications on the structure and energetics of the corresponding H-bonded base pair is available. To fill this gap, we performed quantum mechanics calculations, starting with the analysis of the impact of the 8-aza-7-deaza modification of the adenine skeleton, and we moved then to analyze the impact of the specific substituents on the modified 8-aza-7-deazaadenine. Our analysis indicates that, despite of these severe structural modifications, the H-bonding properties of the modified base pair gratifyingly replicate those of the unmodified base pair. Similar behavior is predicted when the same skeleton modifications are applied to guanine when paired to cytosine. To stress further the H-bonding pairing in the modified adenine–uracil base pair, we explored the impact of strong electron donor and electron withdrawing substituents on the C7 position. Also in this case we found minimal impact on the base pair geometry and energy, confirming the validity of this modification strategy to functionalize RNAs without perturbing its stability and biological functionality.
In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has attracted remarkable attention as a versatile tool to form new CC bonds. The last developed (pre)catalysts show excellent performances, and this achievement has been possible because of continuous experimental and computational efforts to understand the laws controlling the behavior of these systems. This perspective rapidly traces the ideas and discoveries that computational chemistry contributed to the development of these catalysts, with particular emphasis on catalysts presenting a N-heterocyclic carbene ligand.
We report a quantum chemical characterization of the non-natural (synthetic) H-bonded base pair formed by 6-amino-5-nitro-2(1H)-pyridone (Z) and 2-aminoimidazo[1,2-a]-1,3,5-triazin-4(8H)-one (P). The Z:P base pair, orthogonal to the classical G:C base pair, has been introduced into DNA molecules to expand the genetic code. Our results indicate that the Z:P base pair closely mimics the G:C base pair in terms of both structure and stability. To clarify the role of the NO2 group on the C5 position of the Z base, we compared the stability of the Z:P base pair with that of base pairs having different functional groups at the C5 position of Z. Our results indicate that the electron-donating/-withdrawing properties of the group on C5 have a clear impact on the stability of the Z:P base pair, with the strong electron-withdrawing nitro group achieving the largest stabilizing effect on the H-bonding interaction and the strong electron-donating NH2 group destabilizing the Z:P pair by almost 4 kcal/mol. Finally, our gas-phase and in-water calculations confirm that the Z-nitro group reinforces the stacking interaction with its adjacent purine or pyrimidine ring.
Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.
"Classical" MgCl2-supported Ziegler−Natta catalysts (ZNCs) continue to dominate the industrial production of isotactic polypropylene. There is a growing awareness of the inherent competitive edge of these low-cost systems over single-center (primarily metallocene) catalysts and of the potential for further improvement, particularly if deeper insight into the structure of the catalytic surfaces and the mechanisms of their modification by means of electron donors can be achieved. In the framework of a project ultimately aiming at the implementation of ZNCs with known and controlled surface structures, we are revisiting this whole area by using a combination of advanced computational (periodic DFT) and spectroscopic (high-resolution magic-angle-spinning 1H NMR spectroscopy) tools. In this article, we report on the neat MgCl2 matrix and on model MgCl2/electron-donor adducts. The results indicate that the (104) surface, with five-coordinate Mg cations, is the dominant lateral termination in well-formed large crystals, as well as in highly activated MgCl2 samples prepared by ball-milling. In the latter case, a minor fraction of surface Mg sites with a higher extent of coordinative unsaturation [e.g., four-coordinate Mg cations on (110) edges and/or at crystal corners or other defective locations] also appear to be present. RMe2Si(OMe) (R = octadecyl) binds to both types of Mg sites, albeit with different strengths resulting in different mobilities. The less-electron-donating RMeSi(OMe)2, in contrast, binds to the more unsaturated Mg sites only. The approach described herein is currently being extended to MgCl2/TiCln systems, as well as to their adducts with internal and external donors of different natures, strengths, and steric demands.
