Palladium(ii) complexes with chiral organoantimony(iii) ligands. Solution behaviour and solid state structures

The chiral compound (2-Me2NCH2C6H 4)PhSbCl (1) was obtained from (2-Me2NCH2C 6H4)Li and PhSbCl2 in 1:1 molar ratio, while (2-Me2NCH2C6H4)Mes2Sb (2) was prepared from (2-Me2NCH2C6H 4)SbCl2 and MesMgBr in 1:2 molar ratio. The compounds 1 and 2 were used to obtain the Pd(ii)/stibine complexes: [Me2NHCH 2C6H5]+[PdCl3SbCl(Ph) (C6H4CH2NMe2-2)-Sb]- (3) and [PdCl2SbMes2(C6H4CH 2NMe2-2)-N,Sb] (4). All the compounds were characterized by multinuclear NMR spectroscopy in solution, elemental analysis, mass spectrometry and single-crystal X-ray diffraction studies. In compounds 1-3 the coordination geometry around the antimony atom is pseudo-trigonal bipyramidal, while in compound 4 a tetrahedral geometry around the antimony atom is observed. Theoretical calculations at the DFT level on compounds 1-4 were used in order to gain insight into the nature of the coordinative bonds

Fluorescent Orthopalladated Complexes of 4-Aryliden-5(4H)-oxazolones from the Kaede Protein: Synthesis and Characterization

The goal of the work reported here was to amplify the fluorescent properties of 4-aryliden-5(4H)-oxazolones by suppression of the hula-twist non-radiative deactivation pathway. This aim was achieved by simultaneous bonding of a Pd center to the N atom of the heterocycle and the ortho carbon of the arylidene ring. Two different 4-((Z)-arylidene)-2-((E)-styryl)-5(4H)-oxazolones, the structures of which are closely related to the chromophore of the Kaede protein and substituted at the 2- and 4-positions of the arylidene ring (1a OMe; 1b F), were used as starting materials. Oxazolones 1a and 1b were reacted with Pd(OAc)2 to give the corresponding dinuclear orthometalated palladium derivates 2a and 2b by regioselective C-H activation of the ortho-position of the arylidene ring. Reaction of 2a (2b) with LiCl promoted the metathesis of the bridging carboxylate by chloride ligands to afford dinuclear 3a (3b). Mononuclear complexes containing the orthopalladated oxazolone and a variety of ancillary ligands (acetylacetonate (4a, 4b), hydroxyquinolinate (5a), aminoquinoline (6a), bipyridine (7a), phenanthroline (8a)) were prepared from 3a or 3b through metathesis of anionic ligands or substitution of neutral weakly bonded ligands. All species were fully characterized and the X-ray determination of the molecular structure of 7a was carried out. This structure has strongly distorted ligands due to intramolecular interactions. Fluorescence measurements showed an increase in the quantum yield (QY) by up to one order of magnitude on comparing the free oxazolone (QY < 1%) with the palladated oxazolone (QY = 12% for 6a). This fact shows that the coordination of the oxazolone to the palladium efficiently suppresses the hula-twist deactivation pathway

Functionalization and Coordination Effects on the Structural Chemistry of Pendant Arm Derivatives of 1,4,7-trithia-10-aza-cyclododecane ([12]aneNS3)

The effect of different pendant arms on the structural chemistry of the 1,4,7-trithia-10-aza-cyclododecane ([12]aneNS3) macrocycle is discussed in relation to the coordination chemistry of all known functionalized derivatives of [12]aneNS3, which have been structurally characterized

New organophosphorus proligands and amide precursors: Crystal and molecular structures of Ph2P(X)NH(C6H3Pr i2-2,6) (X = O, S) and (OPPh2)(O 2SMe)N(C6H3Pri2-2,6)

The new organophosphorus proligand (OPPh2)(O2SMe)NR (R = C6H3Pri2-2,6)(3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph 2P(O)NR] with MeSO2Cl in a 1:1 molar ratio. The precursor Ph 2P(O)NHR (1), as well as its thio analogue Ph2P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy. The molecular structures of 1-3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N-HX (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn-syn conformation of the O=P(C)2-N-S(C)(=O)2 skeleton. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file

Organotin compounds: organometallic derivatives exhibiting anti-tumour activity

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Organoselenium(II) halides containing the pincer 2,6-(Me2NCH2)2C6H3 ligand – an experimental and theoretical investigation

New organoselenium(II) halides of the type [RSe]+X− [R = 2,6-(Me2NCH2)2C6H3; X = Cl (2), Br (3), I (4)] were prepared by cleavage of the Se–Se bond in R2Se2 (1) with SO2Cl2 followed by halogen exchange when organoselenium chloride was treated with NaBr or KI. The reaction between 2 and R’2MCln resulted in new ionic [RSe]+[R’2MCln+1]− [R’ = 2-(Me2NCH2)C6H4, n = 1, M = Sb (5), Bi (6); R’ = Ph, M = Sb, n = 1 (7) or n = 3 (8)] species. All new compounds were investigated in solution by multinuclear NMR spectroscopy (1H, 13C, 77Se, 2D experiments) and mass spectrometry. The ionic nature of 2 and the antimonates species was confirmed by conductivity studies. The molecular structures of [{2,6-(Me2NCH2)2C6H3}Se]+Cl−·nH2O (2·H2O and 2·2H2O) and [{2,6-(Me2NCH2)2C6H3}Se]+[Ph2SbCl4]− (8), respectively, were established by single-crystal X-ray diffraction, pointing out that the ionic nature of these compounds is also preserved in the solid state, with both nitrogen atoms strongly trans coordinated to the selenium atom of the cation. Theoretical calculations carried out at the DFT level were exploited to investigate the nature of the bonding in compounds 2–4 and the free cation [RSe]+ (2a). A topological analysis based on the theory of Atoms-In-Molecules (AIM) and Electron Localization Function (ELF) jointly to a Natural Bond Orbital (NBO) approach was used to shed light on the effect of the nature of the halogen species X on the bonding within the 3c-4e N–Se–Nmoiety