RESUMO
The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway.
Assuntos
Dióxido de Carbono/química , Carbonatos/química , Terpenos/química , Catálise , Óxido de Etileno/químicaRESUMO
A series of imino- and amino-pyridine ligands based on dihydrobenzofurobenzofuran (BFBF) and methanodibenzodioxocine (DBDOC) backbones have been synthesized. These ligands form exclusively dinuclear complexes with metals such as iron(II) and copper(II). The structures for complexes 15, 16, 18, 19, 20, 21, 23, and 24 were determined by X-ray crystallography. The complexes show large distances for the metal nuclei and different geometries depending on the nature of the metal. An octahedral geometry was observed for the iron(II) complexes, while copper(II) complex 24 showed a distorted trigonal bipyramidal geometry. The iron(II) complexes showed activity as catalysts in the cycloaddition of CO2 to epoxides, obtaining moderate yields of cyclic carbonates.
RESUMO
Iron(III) amino triphenolate complexes with different substituents in the ortho-position of the phenolate moiety (R = H, Me, tBu, or Ph) have been synthesized by the reaction of iron(III) chloride and the sodium salt (Na(3)L(R)) of the requisite ligand. The complexes have been shown to be of either monomeric ([FeL(R)(THF)]) or dimeric ([FeL(R)](2)) nature by a combination of X-ray diffraction, (1)H NMR, solution magnetic susceptibility, and cyclic voltammetry studies. These analytical studies have shown that the monomeric and dimeric [FeL(R)] complexes behave distinctively, and that the dimer stability is a function of the ortho-positioned groups. Both the dimeric as well as monomeric complexes were tested as catalysts for the catalytic cycloaddition of carbon dioxide to oxiranes, and the data show that the monomeric complexes are able to mediate this conversion with significantly higher activities than the dimeric complexes. This difference in reactivity is controlled by the substitution pattern on the ligand L(R), and is in line with the catalytic requisite of binding of the epoxide substrate by the iron(III) center.
Assuntos
Dimerização , Ferro/química , Compostos Organometálicos/química , Fenóis/química , Dióxido de Carbono/química , Eletroquímica , Óxido de Etileno/química , Fenômenos Magnéticos , Compostos Organometálicos/síntese químicaRESUMO
The concept of metal-ligand bifunctionality can be employed for an efficient activation of N-H bonds by well-defined ruthenium amido complexes. An enantioselective catalytic aza-Michael reaction was developed on the basis of this process, which gives rise to indoline ß-amino acids.
RESUMO
The use of olefin metathesis as a construction tool for multimetallic salen-based structures is described. The approach involves mono- and diallyl-functionalized metallosalen complexes that can be directly coupled by metathesis leading to dimetallic species or mixtures of linear and cyclic oligomers. The metathesis of bis-allyl Ni(salen) complexes has been studied in detail. At high concentration it is possible to selectively obtain di-Ni species rather than heavier oligomers while under dilute conditions cyclic rather than linear oligomers are preferentially obtained. A mono-allyl Zn(salphen) complex was efficiently coupled using metathesis to give the di-Zn(salphen) product, which was subsequently transmetalated with a variety of metals to yield dimetallic salens of potential catalytic interest. Finally, a tetranuclear Zn(4) macrocycle was also prepared using buildings blocks obtained by metathesis from commercially available precursors. The methods described herein allow for the facile construction of multi-centered Schiff base complexes of catalytic or supramolecular interest.
RESUMO
A modular and general synthetic method is disclosed for nonsymmetrical heterobimetallic bis-salphen structures starting from a series of synthetically convenient monometalated triimine precursors. This methodology permits the introduction of various combinations of metal ions within the bis-salphen framework potentially useful in multifunctional materials.