Matched/Mismatched interaction of a cyclic hexapeptide with ion pairs containing chiral cations and chiral anions

The binding of a chiral quaternary ammonium ion to a cyclopeptide containing aromatic amino acid subunits is affected not only by the configuration of the cation but also by the configuration of the chiral counterion. Analysis of the binding equilibria shows that complex formation involves interaction of the whole ion pair with the host indicating that steric requirements of the anion influence complex geometry and stability.     

Novel heteroleptic cis-(C--N)2Pd(II) chelates for the preparation of enantiopure planar chiral cyclopalladated 2-[tricarbonyl(eta6-phenyl)chromium]pyridine

In the presence of large amounts of [Me4N]Cl, the reaction of ortho-chloromercurated 2-[(eta6-phenyl)tricarbonylchromium]pyridine with mu-chloro cyclopalladated aromatic compounds yields a series of new heteroleptic heterodinuclear cis-(C--N)2Pd(II) complexes, which are valuable precursors of planar chiral cyclopalladated (eta6-arene)Cr(CO)3 complexes.     

Rhodium(II)-Catalyzed CH Insertions with {[(4-Nitrophenyl)sulfonyl]imino}phenyl-λ3-iodane

The [Rh₂(OAc)₄]-catalyzed decomposition of {[(4-nitrophenyl)sulfonyl]imino}phenyl-λ³-iodane (NsN?IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhanced by electron-releasing substituents and decreased by steric hindrance. Aziridination competed with allylic insertion with olefinic substrates. The insertion reaction proceeded with retention of configuration. With chiral Rh^II catalysts, a modest asymmetric induction was observed. A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.     

Synthesis and characterization of the mononuclear oxovanadium-disulphide compound [N(Bu)4][V(O)(S2)2bipy]

Summary The reaction of NH₄VO₃ with S ₂ ^-2 in ammonia in the presence of 2,2-bipyridine (bipy) and [N(Bu)₄]Br gives the mononuclear compound [N(Bu)₄][V(O)(S₂)₂bipy] (1) isolated at room temperature in crystalline form. The X-ray crystal structure determination shows that the vanadium(V) centre is ligated by four sulphur atoms and a nitrogen atom of the bipy ligand forming the equatorial plane of pentagonal bipyramid, an oxygen and the remaining nitrogen atom of the bipy occupying the two apices of the bipyramid.     

New Metal Oxamates as Precursors of Low-Dimensional Heterobimetallics

The goal of this work was to synthesize new molecular bricks which could be used as precursors of heterobimetallic low-dimensional compounds. Along this line, four compounds have been synthesized and structurally characterized, namely (NBu(4))(2)[Ni(Cl(2)opba)] (1), (NBu(4))(2)[Cu(Cl(2)opba)] (2), (NBu(4))(5)[Mn(Cl(2)opba)(DMSO)(2)](4) (3), and Cu(en)(2)[Mn(Cl(2)opba)(H(2)O)(2)](2).2DMSO (4), with Cl(2)opba = (4,5-dichloro-o-phenylene)bis(oxamato), NBu(4) = tetra-n-butylammonium, en = ethylenediamine, and DMSO = dimethyl sulfoxide. Compounds 1 and 2 are isostructural; they crystallize in the monoclinic system, space group C2/c, Z = 4, with a = 18.708(2) ?, b = 17.525(2) ?, c = 14.763(9) ?, and beta = 92.03(4) degrees for 1 and a = 18.928(2) ?, b = 17.634(2) ?, c = 14.704(9) ?, and beta = 92.38(3) degrees for 2. 3 crystallizes in the tetragonal system, space group P&fourmacr;2(1)c, Z = 2, with a = 26.295(10) ? and c = 12.342(7) ?. The structure shows a random occupation of the metal site by Mn(III) and Mn(II) ions in 3/4 and 1/4 ratios, respectively. 4 crystallizes in the triclinic system, space group P&onemacr;, Z = 1, with a = 7.066(7) ?, b = 11.844(1) ?, c = 14.292(5) ?, alpha = 105.64(2) degrees, beta = 97.67(5) degrees, and gamma = 102.13(3) degrees. The structure consists of Mn(III)Cu(II)Mn(III) trinuclear species, with Cu-O-Mn bridges involving oxygen atoms of the oxamato groups already linked to the metal atom. The magnetic properties of compounds 1-4 have been investigated and quantitatively interpreted. For 3, this magnetic investigation has been performed on a single crystal, which allows us to determine unambiguously the sign of the axial zero-field splitting parameter for the Mn(III) ion. The potentialities of these new molecular bricks have been discussed.     

Novel Mo(V)-dithiolene compounds: characterization of nonsymmetric dithiolene complexes by electrospray ionization mass spectrometry

Three new Mo(V) dithiolene compounds have been synthesized by addition of alkynes ((Me(3)Si)(2)C(2) (TMSA), (Me(3)Si)(2)C(4), and (Ph)(2)C(4) to MoO(2)S(2)(2-) in a MeOH/NH(3) mixture: [Mo(2)(O)(2)(mu-S)(2)(eta(2)-S(2))(eta(2)-S(2)C(2)H(2))](2)(-) 1, [Mo(2)(O)(X)(mu-S)(2)(eta(2)-S(2))(eta(2)-S(2)C(2)Ph(C(2)Ph))](2-) 2 (X = O or S), and [Mo(2)(O)(2)(mu-S)(2)(eta(2)-S(2))(eta(2)-S(2)C(2)H(C(2)H))](2-) 3. The structure of 1 as determined by single-crystal X-ray diffraction study (space group Pbca, a = 13.3148(1) A, b = 15.7467(4) A, c = 28.4108(7) A, V = 5956.7(2) A(3)) is discussed. 2 and 3 have been identified by ESMS (electrospray mass spectrometry), (1)H NMR, (13)C NMR, and infrared spectroscopies. This investigation completes our previous study devoted to the addition of DPA (C(2)Ph(2)) to MoO(2)S(2)(2-) which led to [Mo(2)(O)(X)(mu-S)(2)(eta(2)-S(2))(eta(2)-S(2)C(2)Ph(2))](2-) 4 (X = O or S). A reaction scheme is proposed to explain the formation of the different species present in solution. The reactivity of the remaining nucleophilic site of these complexes (eta(2)-S(2)) toward dicarbomethoxyacetylene (DMA) is also discussed.     

Characterization of polyoxometalate/polymer photo-composites: A toolbox for the photodegradation of organic pollutants

Different inorganic/organic photocomposites based on polyoxometalate (POM) nanoparticles have been developed for photocatalytic applications. Currently, polyoxometalate nanoparticles have been successfully in-situ embedded into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The proposed POM/polymer photocomposites have been characterized using complementary techniques for a better understanding of their photocatalytic activity. Interestingly, the obtained photocomposites exhibit high rigidity, excellent thermal stability, a non-negligible porosity and new functionalities such as light reactivity and redox properties. Moreover, developed composites showed efficient catalytic activity for the color removal of aqueous solutions of erythrosine and rose Bengal under Light Emitting Diodes LED@375 nm irradiation reaching 80 and 90% as a final color removal, respectively.     

Easy Preparation of 1,3-Di-tert-Butylbenzene and Some Derivatives Thereof

1,3-Di-tert-butylbenzene (4) can conveniently be prepared from 1-bromo-3,5-di-tert-butylbenzene (2) which, in turn, is obtained from the easily available 1,3,5-tri-tert-butylbenzene (1). The use of 4 is illustrated by the preparation of the arylphosphines 6 and 7.