Search results for "Adduct"

Catalytic aminomercuration of olefins in a tandem aminomercuration-deoxymercuration; One-step synthesis of secondary n-arylallylamines from allylalco…

1990

Abstract Allyl alcohols react with primary aromatic amines and stoichiometric amounts of mercury(II) tetrafluoroborate to give mixtures of mono- and diallyl anilines. However, the use of the tandem aminomercuration-deoxymercuration promoted by catalytic mercury(II) tetrafluoroborate allows to perform regiospecifically the monoallylation reaction with very high yields. A mechanism is proposed to account for the observed results.

Analysis of the Decarboxylation Step in Mammalian Histidine Decarboxylase

2008

We report a hybrid quantum mechanics/molecular mechanics theoretical study on the reaction mechanism of mammalian histidine decarboxylase that allows us to obtain valuable insights on the structure of the cofactor-substrate adduct (external aldimine) in the active site of rat histidine decarboxylase. By means of molecular dynamics simulations, we traced the potential of mean force corresponding to the decarboxylation reaction of the adduct both in the active site of the enzyme and in aqueous solution. By comparing this process in both media, we have identified the key electrostatic interactions that explain the lowering of the free energy barrier in the enzyme. Our analysis also offers a va…

DNA Oxidation Photoinduced by Norharmane Rhenium(I) Polypyridyl Complexes: Effect of the Bidentate N,N′-Ligands on the Damage Profile

2018

Re(I)--polypyridyl complexes have interesting and distinctive photochemical and photosensitizing properties. This work describes the capability to induce (or photoinduce) DNA damage of three Re(I)-complexes with a naturally occurring alkaloid called norharmane (nHo) as ligand: [Re(CO)₃ (nHo)(L)]CF₃ SO₃ where L=2,2'-bipyridine (ReBpy), phenanthroline (RePhen) or dipyrido[3,2-a:2',3'-c]phenazine (ReDppz). The interaction of the complexes with DNA was investigated by steady-state and time-resolved spectroscopy. Data show that the mode and strength of interaction depend on the chemical structure of the bidentate ligand. The complexes show a major static contribution to the overall interaction, …

X-ray crystal structures of copper(II) and cobalt(II) complexes with Schiff base ligands. Reactivity towards dioxygen

2003

Copper(II) and cobalt(II) Schiff base complexes with derivatives of the pentadentate ligand bis(salicylideneimino-3-propyl)amine [H2salDPT] have been prepared. The X-ray crystal structures of the copper(II) complexes Cu[salDPT] and Cu[sal(n-propyltrimethylsilyl)DPT] were determined and revealed five-coordination at the metal centre in both cases. The 1 ∶ 1 dioxygen adduct of Co[sal(n-propyltrimethylsilyl)DPT] was also isolated and its X-ray molecular structure determined.

Synthesis, X-ray structure and magnetic properties of the azido adducts of quadridentate Schiff base manganese(III) complexes

2004

Abstract Two new azido derivatives of quadridentate Schiff base manganese(III) complexes have been synthesized and characterized structurally and magnetically. X-ray structure analysis revealed that both complexes viz. [Mn2(L1)2(N3)2] (1) and [Mn2(L2)2(N3)2] (2), where H2L1=N,N′-(1,1-dimethylethylene)-bis-(salicylaldiimine) and H2L2=bis(o-hydroxyacetophenone)-ethylenediimine exist as phenoxo-bridged dimer. The magnetic susceptibility of the complexes has been measured in the 5–300 K range. At room temperature the MnIII ions in complexes 1 and 2 possess an S=4 ground state. The global magnetic interaction in complex 1 is found to be ferromagnetic, while for complex 2 it is anti-ferromagnetic.

Sunlight-induced functionalisation reactions of heteroaromatic bases with aldehydes in the presence of TiO2: A hypothesis on the mechanism

2007

In previous studies we reported a new photocatalytic system involving polycrystalline TiO2 for the selective functionalisation of heteroaromatic bases with ethers and amides. In order to extend the applications of this new reaction and to better understand the mechanism involved, we have examined aromatic and aliphatic aldehydes as acyl radical sources for the nucleophilic addition to protonated N-heteroarenes in acetonitrile as the solvent and TiO2/H2O2 as the photocatalytic system. Acyl radicals may undergo decarbonylation to yield the corresponding alkyl radicals. Acyl/alkyl derivative ratios depend on the nature of the aldehydes, and present a different distribution from that obtained i…

Solvent induced polymorphism and pseudopolymorphism among fullerene C60organic adducts

2011

Synthesis and Characterization of Adducts Derived from the syn-Diastereomer of Benzo[a]pyrene 7,8-Dihydrodiol 9,10-Epoxide and the 5‘-d(CCTATAGATATCC…

1996

5'-d(CCTATAGATATCC) was reacted with each syn-enantiomer of trans-7,8-dihydroxy 9,10-epoxy 7,8,9,10-tetrahydrobenzo[a]pyrene (syn-BPDE). The (-)-enantiomer yielded one dominating adduct, whereas the (+)-enantiomer resulted in two major adducts. As indicated by optical spectroscopic methods, the major adduct derived from both (-)- and (+)-syn-BPDE involves cis addition of the C-10 position of the diol epoxide to the exocyclic amino group of deoxyguanosine [(-)-syn-BPDEc-N2-dG and (+)-syn-BPDEc-N2-dG, respectively], whereas the minor (+)-syn-BPDE adduct is identical to a trans adduct [(+)-syn-BPDEt-N2-dG]. The cis adducts as well as the (+)-syn-BPDEt-N2-dG adduct are chemically stable for sev…

Mono-, di- and tri-nuclear Ni(II) complexes of N-, O-donor ligands: structural diversity and reactivity

2002

A series of mono-, di- and tri-nuclear Ni(II) complexes of N, O-donating molecules possessing ---H2C---NH--- and ---HC=N--- moieties have been synthesized and characterized and the structures have been determined by single crystal X-ray diffraction. All these exhibited interesting molecular packing in their crystal lattices. Di-nuclear complexes were found to be cleaved in pyridine to result in mononuclear ones with additional coordinations being provided by pyridine. Di-nuclear complexes were found to form urea adducts as demonstrated based on absorption and vibrational studies.

Strukturen von [Me4Sb]2[MeSbI4]MeSbI2, und [Me4Sb]I. Darstellung von Me3Sb · MeSbI2 und farbwechsel bei Me4Sb2 · Me2SbBr

1992

Abstract The crystal structures of the complex [Me 4 Sb] 2 [MeSbI 4 ] ( 1 ) and its precursors MeSbI 2 ( 2 ) and [Me 4 Sb]I ( 3 ) are reported. In 1 there are tetrahedral cations and square pyramidal anions with Sb-I distances of 290–320 pm. The structure of 2 contains MeSbI 2 molecules. They associate via iodine bridges to form linear chains with alternating short and long Sb-I distances. The coordination around antimony is distorted tetragonal pyramidal. The tetrahedral coordination of the ions in 3 results in the formation of a wurtzite type structure with antimony-iodine distances of 406 and 435 pm. The novel adducts Me 3 Sb·Me 2 SbI 2 ( 4 ) and Me 2 SbSbMe 2 ·Me 2 SbBr ( 5 ) are formed…