Characterizing the Effects of a "Switchable Water" Additive on the Aqueous Solubility of Small Molecules.

"Switchable water" is an aqueous solution containing a water-soluble amine additive that exhibits CO -switchable properties, such as large changes in ionic strength, by forming an ammonium bicarbonate salt. Switchable water has been used to reversibly "salt-out" organic compounds from water. This study explores the salting out of several compounds in switchable water when CO is present and also explores the solubility of small molecules in switchable water, compared to pure water, when CO is absent.

Organoactinides promote the dimerization of aldehydes: scope, kinetics, thermodynamics, and calculation studies.

Surprising catalytic activities have been found for the actinide complexes Cp*(2)ThMe(2) (1), Th(NEtMe)(4) (2), and Me(2)SiCp''(2)Th(C(4)H(9))(2) (3) toward oxygenated substrates. During the catalytic dimerization of benzaldehydes to their corresponding esters, complexes 1 and 2 gave 65 and 85% yield in 48 h, respectively, while the geometry-constrained complex 3 gave 96% yield in 24 h. Exploring the effect of substituents on benzaldehyde, it has been found that, in general, electron-withdrawing groups facilitate the reaction.

Recent advances in organothorium and organouranium catalysis.

In this critical review we summarize the latest results obtained during the last decade concerning the catalytic activities of organoactinide complexes. We begin with a brief summary of the synthesis and characterization of uranium and thorium complexes that later will be used as catalysts for demanding chemical transformations. Hydroamination, hydrosilylation of terminal alkynes, coupling of terminal alkynes with isonitriles, catalytic reduction of azides and hydrazines, ring opening polymerization of cyclic esters and polymerization of alpha-olefins are covered in this review (118 references).

Catalytic coupling of terminal alkynes with isonitriles promoted by organoactinide complexes.

The coupling reaction of terminal alkynes and tert-butylisonitrile to yield substituted alpha,beta-acetylenic aldimines is catalyzed by the organoactinide neutral complexes Cp*2AnMe2 (Cp* = C5Me5, An = Th, U) and the cationic complex [(Et2N)3U][BPh4]. The reaction proceeds by a 1,1-insertion of the isonitrile into the metal-acetylide bond. Additional insertion products can be obtained by altering the catalyst and the reactant ratios.

Formation of inclusion organoactinide complexes with boron-containing macrocycles.

Reaction of the organoactinide complexes (C5Me5)2AnMe2 (An = Th, U) with catecholborane yields an inclusion complex where the actinide is encapsulated inside a 15-membered, hexaoxo, trianionic macrocycle built from alternating catechol and catecholborate fragments. In the presence of LiOH, a dimer of two encapsulated actinide macrocycles is formed. The X-ray molecular structure for all the complexes is presented.