P(V)-bis(amidophenolate) ligand cooperation: stoichiometric CO-bond cleavage in aldehydes and ketones.

The cooperation between a geometrically constrained, highly electrophilic phosphorus(V) center, and an electronically rich tetradentate bis(amidophenolate) ligand enables the cleavage of the CO bond from typical aldehydes and ketones delivering iminio phosphoramidate species. The amphiphilic nature of these products, which is demonstrated through their reaction with typical Lewis acids and bases, enables their use as a mild source of silylium cations from silanes, allowing the selective reductive coupling of aldehydes to ethers under catalytic conditions.

Cooperation between p-Block Elements and Redox-Active Ligands: Stoichiometric and Catalytic Transformations.

The relevance acquired by redox-active ligands in modern catalysis stems from their facile delivery and acceptance of electrons, either to the metal they coordinate to, or directly to an incoming substrate that also binds the central metal. Doing that, they generate coordinated radicals and provide access to more than one spin state during the catalytic cycle. As a consequence, the new reaction barriers are reduced when compared to similar processes that are restricted to a single spin surface. The principles that govern this genuine approach to catalyst design are well-established, and their implementation has allowed the development of synthetically useful catalytic transformations; however, the extension of the concept to species in which p-block elements take the role of central atoms remains largely underdeveloped. Through discussion of the key achievements and recent progress, this Concept Article highlights this original approach to designing (organo)catalysts, discloses the progress achieved, and also reveals the many shortcomings that still exist in the field.

Ligand-Enabled Disproportionation of 1,2-Diphenylhydrazine at a PV -Center.

We present herein the synthesis of a nearly square-pyramidal chlorophosphorane supported by the tetradentate bis(amidophenolate) ligand, N,N'-bis(3,5-di-tert-butyl-2-phenoxy)-1,2-phenylenediamide. After chloride abstraction the resulting phosphonium cation efficiently promotes the disproportionation of 1,2-diphenylhydrazine to aniline and azobenzene. Mechanistic studies, spectroscopic analyses and theoretical calculations suggest that this unprecedented reactivity mode for PV -centres is induced by the high electrophilicity at the cationic PV -center, which originates from the geometry constraints imposed by the rigid pincer ligand, combined with the ability of the o-amidophenolate moieties to act as electron reservoir. This study illustrates the promising role of cooperativity between redox-active ligands and phosphorus for the design of organocatalysts able to promote redox processes.

Synthesis of 6H-Benzo[c]chromene Scaffolds from O-Benzylated Phenols through a C-H Sulfenylation/Radical Cyclization Sequence.

S-Aryl dibenzothiophenium salts, obtained through a highly regioselective C-H sulfenylation of o-benzyl-protected phenols, are used as precursors of 6H-benzo[c]chromenes. The reaction starts with a photocatalytically triggered single-electron transfer to the sulfonium salt, which promotes the formation of an aryl radical via selective mesolitic cleavage of the S-Arexo bond. Mechanistic studies reveal that this initial radical species cyclizes following a kinetically favored 5-exo-trig pathway. Subsequent ring expansion, favored by rearomatization, delivers the desired tricyclic systems.

Circulation time and body distribution of 14C-labeled amino-modified polystyrene nanoparticles in mice.

Commercially available amino-modified polystyrene particles of size range 100-1,000 nm were radioactively labeled with [14C]-formaldehyde. A study of the circulation time and body distribution of these particles was carried out in mice. The animals were sacrificed at 1-30 min after intravenous administration of the particles. The blood and organ (liver, spleen, lung) profiles of particles were determined by measuring their radioactivity by means of liquid scintillation counting. In general, larger particles were eliminated from blood faster than smaller particles. The blood elimination half-life ranged from 1.36 to 4.92 min. The particles were mainly taken up by the liver with larger particles being taken up faster than the smaller particles. At 30 min after injection, 60% of the administered 100 nm particles were present in the liver, whereas 85% of the 100 nm particles were found in the liver. Accumulation in the spleen was 1-3% of the total number administered in the entire size range. At 1 min after injection, less than 3% of the total dose administered was present in the lungs and this value decreased rapidly to less than 1% at 2 min. The only exception occurred for 100 nm, where 2.35% was present in the lungs at 2 min after injection.

Nucleotide sequences and mutational analysis of the structural genes for nitrogenase 2 of Azotobacter vinelandii.

The nucleotide sequence (6,559 base pairs) of the genomic region containing the structural genes for nitrogenase 2 (V nitrogenase) from Azotobacter vinelandii was determined. The open reading frames present in this region are organized into two transcriptional units. One contains vnfH (encoding dinitrogenase reductase 2) and a ferredoxinlike open reading frame (Fd). The second one includes vnfD (encoding the alpha subunit of dinitrogenase 2), vnfG (encoding a product similar to the delta subunit of dinitrogenase 2 from A. chroococcum), and vnfK (encoding the beta subunit of dinitrogenase 2). The 5'-flanking regions of vnfH and vnfD contain sequences similar to ntrA-dependent promoters. This gene arrangement allows independent expression of vnfH-Fd and vnfDGK. Mutant strains (CA80 and CA11.80) carrying an insertion in vnfH are still able to synthesize the alpha and beta subunits of dinitrogenase 2 when grown in N-free, Mo-deficient, V-containing medium. A strain (RP1.11) carrying a deletion-plus-insertion mutation in the vnfDGK region produced only dinitrogenase reductase 2.