Search results for "SMETA"

Stereoselective Conjugate Addition of Mixed Organoaluminum Reagents to ?,?-Unsaturated N-Acyloxazolidinones Derived from Carbohydrates.

2005

The stereoselective synthesis of β-branched carboxylic acid derivatives was accomplished by conjugate addition of mixed organoaluminum reagents to chiral α,β-unsaturated N-acyloxazolidinones. Mixed organoaluminum reagentswere generated in situ by transmetalation of Grignard or organolithium compounds with methylaluminum dichloride. Efficient stereocontrol was achieved using different bicyclic glycosamine-derived oxazolidinones, yielding alternatively (R)- or (S)-configured β-branched carboxylic acid derivatives.

Coordination versatility of pyridine-functionalized N-heterocyclic carbenes: a detailed study of the different activation procedures. Characterizatio…

2005

Three different reaction procedures for the coordination of N-n-butyl-N'-(2-pyridylmethyl)imidazolium salt have produced new N-heterocyclic complexes of Rh and Ir. The direct reaction of the imidazolium salt with [IrCl(cod)](2) provides a NHC-Ir(III)-H complex, while transmetalation from a silver-NHC complex and deprotonation with NEt(3) give new NHC complexes of M(I) and M(III) when reacting with [MCl(cod)](2) or [MCl(coe)(2)](2) (M = Rh, Ir). The crystal structures of the biscarbene Rh(III) and Ir(III) complexes are described. The catalytic properties of the compounds obtained have been tested in the hydrosilylation of acetylenes, the cyclization of acetylenic carboxylic acids, and hydrog…

Electrical Behaviour of Heterobimetallic [MM′(EtCS2)4] (MM′=NiPd, NiPt, PdPt) and MM′X-Chain Polymers [PtM(EtCS2)4I] (M=Ni, Pd)

2012

Herein, we report the isolation of new heterobimetallic complexes [Ni0.6Pd1.4ACHTUNGTRENUNG(EtCS2)4] (1), [NiPtACHTUNGTRENUNG(EtCS2)4] (2) and [Pd0.4Pt1.6ACHTUNGTRENUNG(EtCS2)4] (3), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM'X monodimensional chains [Ni0.6Pt1.4ACHTUNGTRENUNG(EtCS2)4I] (4) and [Ni0.1Pd0.3Pt1.6ACHTUNGTRENUNG(EtCS2)4I] (5). The physical properties of these systems were investigated and the chain structures 4 and 5 were found to be reminiscent of the parent [Pt2ACHTUNGTRENUNG(EtCS2)4I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spont…

Benzodiselenagermoles and spirobisbenzodiselenagermoles

1993

Synthesis of benzodiselenagermoles and bisbenzodiselenagermoles was carried out by transmetallation group 4 group 14 between diselenophenylenezirconocenes and dialkyl-, diaryl- or alkylaryldichlorogermanes, aryltrichlorogermane or germanium tetrachloride. The new compounds were studied by 1H, 77Se NMR and mass spectrometry. In the case of compounds with substituted phenyl groups, double irradiation and 2D NMR experiments were performed to determine the chemical shifts of the two selenium atoms. The crystal structure of a spirobisbenzodiselenagermole has been established by X-ray diffraction analysis.

Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand

2018

Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η 2 -cod), 3. In reaction with GeCl2, this produced (2)NiGeCl2, 4, featuring a T-shaped Ni(0) and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2, in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2Ni(cod) complexes 9 and 10, as well as (NHC)2GeCl2 derivative 11, incor…

New applications of zoobenthos measurements for risk assessment of chemicals in aquatic ecosystems

2015

Artikkeliväitöskirja. Yhteenveto-osa ja viisi artikkelia. (Artikkelit eivät avoimesti saatavilla.) Article dissertation. An introduction and five articles (not available in this version). Benthic animals in aquatic ecosystems suffer from various anthropogenic pollutants. A challenge in risk assessment of chemicals in aquatic ecosystems (i.e. ecological risk assessment) has been to balance cost-efficiency and effectiveness in detecting early warning signals of chemicals. In this study, hyperspectral imaging and behavioural measurements were evaluated as novel applications for detecting chemical effects on benthic animals, and the reliability of the incidence of chironomid morphological defor…

Effect of Mg2+ ions on competitive metal ions adsorption/desorption on magnesium ferrite : mechanism, reusability and stability studies

2021

The adsorption behavior of magnesium ferrite in single- and multicomponent metal ions solutions in the presence of Mg2+ ions were studied. A dramatic decrease in the adsorption capacity of magnesium ferrite towards Mn2+, Co2+, and Ni2+ ions for comparison study of single- and multicomponent solutions was established. The affinity of the sorbent in accordance with the maximum sorption capacities increases in the following order Cu2+ > Co2+ > Ni2+ > Mn2+. High efficiency of magnesium ferrite regeneration (~100%) with aqueous solutions of magnesium chloride in the concentration range of 0.001-0.1 M was shown. The low degree of toxic metal ions desorption combined with XRD, IR spectroscopy, and…

Polimeryzacja propylenu katalizowana metaloorganicznymi kompleksami z chiralnymi ligandami salenowymi

2007

Kadmiumaltistuksen havaitseminen Hydropsyche pellucidula -vesiperhostoukilla (Trichoptera: Hydropsychidae) hyperspektrikuvantamisen ja kidusvaurioide…

2017

Metallipäästöt aiheuttavat vesistöissä eliöyhteisöille monenlaisia haittavaikutuksia, joita voidaan tutkia bioindikaattori- eli ilmentäjälajimenetelmin. Vesiperhostoukkia (Trichoptera) on käytetty virtavesien metallisaastumisen indikaattoreina, sillä ne kestävät metallialtistusta suhteellisen hyvin, mutta altistuksen seurauksena toukilla voi esiintyä morfologisia muutoksia, kuten kidusvaurioita tai pintakudoksen tummumista. Koska toisaalta vierasaineiden kudospitoisuusmittaus on usein työlästä ja toisaalta rakenteellisten muutosten arviointi altis subjektiiviselle harhalle, tavoitteenani oli kehittää objektiivinen ja kustannustehokas tapa selvittää metallialtistusta ja sen vaikutuksia pohja…

Hexagonal Microparticles from Hierarchical Self-Organization of Chiral Trigonal Pd3L6 Macrotetracycles

2021

Construction of structurally complex architectures using inherently chiral, asymmetric, or multi-heterotopic ligands is a major challenge in metallosupramolecular chemistry. Moreover, the hierarchical self-organization of such complexes is unique. Here, we introduce a water-soluble, facially amphiphilic, amphoteric, chiral, asymmetric, and hetero-tritopic ligand derived from natural bile acid, ursodeoxycholic acid. We show that via the supramolecular transmetalation reaction, using nitrates of Cu(II) or Fe(III), and subsequently Pd(II), a superchiral Pd3L6 complex can be obtained. Even though several possible constitutional isomers of Pd3L6 could be formed, because of the ligand asymmetry a…