The borrowing hydrogen (BH) principle, also called hydrogen auto-transfer, is a powerful approach which combines transfer hydrogenation (avoiding the direct use of molecular hydrogen) with one or more intermediate reactions to synthesize more complex molecules without the need for tedious separation or isolation processes. The strategy which usually relies on three steps, (i) dehydrogenation, (ii) intermediate reaction, and (iii) hydrogenation, is an excellent and well-recognized process from the synthetic, economic, and environmental point of view. In this context, the objective of the present review is to give a global overview on the topic starting from those contributions published prior to the emergence of the BH concept to the most recent and current research under the term of BH catalysis. Two main subareas of the topic (homogeneous and heterogeneous catalysis) have been identified, from which three subheadings based on the source of the electrophile (alkanes, alcohols, and amines) have been consid...

/pdf/advances-in-one-pot-synthesis-through-borrowing-hydrogen-5955xy1911.pdf

Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis

We review the nonaqueous precursor chemistry of the group 4 metals to gain insight into the formation of their oxo clusters and colloidal oxide nanocrystals. We first describe the properties and structures of titanium, zirconium, and hafnium oxides. Second, we introduce the different precursors that are used in the synthesis of oxo clusters and oxide nanocrystals. We review the structures of group 4 metal halides and alkoxides and their reactivity toward alcohols, carboxylic acids, etc. Third, we discuss fully condensed and atomically precise metal oxo clusters that could serve as nanocrystal models. By comparing the reaction conditions and reagents, we provide insight into the relationship between the cluster structure and the nature of the carboxylate capping ligands. We also briefly discuss the use of oxo clusters. Finally, we review the nonaqueous synthesis of group 4 oxide nanocrystals, including both surfactant-free and surfactant-assisted syntheses. We focus on their precursor chemistry and surface chemistry. By putting these results together, we connect the dots and obtain more insight into the fascinating chemistry of the group 4 metals. At the same time, we also identify gaps in our knowledge and thus areas for future research.

/pdf/nonaqueous-chemistry-of-group-4-oxo-clusters-and-colloidal-225f8ww7.pdf

Nonaqueous Chemistry of Group 4 Oxo Clusters and Colloidal Metal Oxide Nanocrystals.

Formation of carboalkoxyiridium complexes by carbonylation of alkoxyiridium complexes and the crystal structure of trans-PhOIr(CO)(PPh 3 ) 2

The worldwide increase in biodiesel production has created a major market for sodium methoxide, as a catalyst in the transesterification of vegetable oils. This work evaluates different methods for the manufacture of sodium methoxide, diluted in methanol. Alternative process designs are reviewed, and the most promising solutions are modeled in Aspen Plus, including their phase and chemical equilibria. Economic indicators are incorporated in a comparative profitability analysis that includes a risk evaluation with Monte Carlo simulations. The results show that the methods of manufacturing sodium methoxide from sodium metal (process II) and from sodium hydroxide (process III) are the most competitive alternatives, although each can be preferred in different contexts. Process III has a better chance of profitability (41%) than process II (34%), where the latter can be affected by higher raw-material costs and the first is more sensitive to variations in the utility and capital costs.

Process Simulation and Techno-Economic Analysis of the Production of Sodium Methoxide

The ultrastructural control of materials through sol-gel processes offers significant promise for the achievement of reliable performance in ceramics, glass and composites. Several examples of new structural, optical and electromagnetic materials with superior and unique properties are presented based on maximal homogeneity or heterogeneity attained through understanding of the fundamental chemistry. New concepts such as ceramic molecular composites and optically active gels have been derived through polymer, physical and synthetic chemistry. Scaling calculations based on molecular orbital calculations for prediction of the silanol polymerization mechanism, and hierarchical clustering predictions for the sol-gel derived ultrastructures are presented. The application of polymeric network theory to the design of gel ultrastructures is presented.

Better ceramics through chemistry

3 – Heterometallic Alkoxides

2 – Homometallic Alkoxides

4 – X-Ray Crystal Structures of Alkoxo Metal Compounds

7 – Industrial Applications

6 – Metal Aryloxides

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