Search results for " Complexes"
showing 10 items of 818 documents
Computational Analysis of n→π* Back-Bonding in Metallylene-Isocyanide Complexes R2MCNR′ (M = Si, Ge, Sn; R = tBu, Ph; R′ = Me, tBu, Ph)
2013
A detailed computational investigation of orbital interactions in metal–carbon bonds of metallylene–isocyanide adducts of the type R2MCNR′ (M = Si, Ge, Sn; R, R′ = alkyl, aryl) was performed using density functional theory and different methods based on energy decomposition analysis. Similar analyses have not been carried out before for metal complexes of isocyanides, even though the related carbonyl complexes have been under intense investigations throughout the years. The results of our work reveal that the relative importance of π-type back-bonding interactions in these systems increases in the sequence Sn < Ge ≪ Si, and in contrast to some earlier assumptions, the π-component cannot be …
Synthesis, X-ray structures and redox behaviour of the group 14 bis-boraamidinates M[PhB(μ-N-t-Bu)2]2 (M = Ge, Sn) and Li2M[PhB(μ-N-t-Bu)2]2 (M = Sn,…
2009
The solid-state structures of the complexes M[PhB(μ-N-t-Bu)2]2 (1a, M= Ge; 1b, M = Sn) were determined to be spirocyclic with two orthogonal boraamidinate (bam) ligands N,N′-chelated to the group 14 centre. Oxidation of 1b with SO2Cl2 afforded the thermally unstable, blue radical cation {Sn[PhB(μ-N-t-Bu)2]2}•+, identified by electron paramagnetic resonance (EPR) spectroscopy supported by density functional theory (DFT) calculations, whereas the germanium analogue 1a was inert towards SO2Cl2. The reaction between Li2[PhB(μ-N-t-Bu)2]2 and SnCl2 or PbI2 in 2:1 molar ratio in diethyl ether produced the novel heterotrimetallic complexes Li2Sn[PhB(μ-N-t-Bu)2]2 (2b) and (Et2O·Li)LiPb[PhB(μ-N-t-Bu)…
Cyclotriveratrylene-Containing Porphyrins
2016
International audience; The C-3-symmetric cyclotriveratrylene (CTV) was covalently bonded via click chemistry to 1, 2, 3, and 6 zinc(II) porphyrin units to various host for C-60. The binding constants, Ka, were measured from the quenching of the porphyrin fluorescence by C-60. These constants vary between 400 and 4000 M-1 and are considered weak. Computer modeling demonstrated that the zinc(II) porphyrin units, [Zn], exhibit a strong tendency to occupy the CTV cavity, hence blocking the access for C-60 to land on this site. Instead, the pincer of the type [Zn]-[Zn] and in one case [Zn]-CTV, were found to be the most probable geometry to promote host-guest associations in these systems.
Badanie właściwości inkluzyjnych p-tert-butylokaliksarenów metodą inwersyjnej chromatografii gazowej
2007
Metodą QSRR scharakteryzowano właściwości inkluzyjne p-tert-butylokaliksarenów o 4, 6 i 8 merach w cyklu oraz ich octanów, wykorzystując do tego celu inwersyjną chromatografię gazową. W badaniach zastosowano przy tym dwa szeregi homologiczne solutów - alkohole alifatyczne oraz benzen i jego homologi. Stwierdzono, że zdolności inkluzyjne w znacznym stopniu zależą od wymiarów luki molekularnej cyklomeru. Zamiana w kaliksarenach grup wodorotlenowych na octanowe nie wywiera natomiast istotnego wpływu na możliwości tworzenia kompleksów typu gość-gospodarz. Wyniki uzyskane metodą QSRR potwierdzono wyznaczonymi wartościami indeksów Kovátsa.
Badanie metodą inwersyjnej chromatografii gazowej wpływu wielkości podstawnika na właściwości inkluzyjne kaliksarenów
2009
Badano wpływ wielkości alifatycznego podstawnika na zdolności inkluzyjne kaliksarenów {kaliks[4]arenu(K4), p-izopropylokaliks[4]arenu (IPK4) i p-tert-butylokaliks[4]arenu (TBK4)}. Oceny wpływu dokonywano za pomocą metody QSRR przy użyciu inwersyjnej chromatografii gazowej. W charakterze solutów użyto szeregu alifatycznych alkoholi, homologów benzenu i homologów pirydyny. Na podstawie indeksów retencji Kovatsa i wykresów zależności właściwej objętości retencji od temperatury wrzenia [Vg=f(Tw)] stwierdzono, że tylko podstawione kaliksareny wykazują właściwości inkluzyjne w stosunku do niższych alkoholi.
Influence of Anion and Cation Structure of Ionic Liquids on Carboxylic Acids Extraction
2019
A recently proposed new mechanism and a model of reactive extraction of carboxylic acids by hydrophobic ionic liquids (ILs) was tested on five systems from published as well as from new equilibrium data on liquid-liquid extraction of butyric and lactic acids (BA and LA) from aqueous solutions. Two phosphonium and one ammonium ILs were used. The model describes experimental data for all systems with a good fit. The mechanism of acid extraction by ILs is very similar for all tested systems. This indicates a more general validity of the developed model. The model allows deeper understanding of regularities in carboxylic acid extraction by hydrophobic ILs. Stability constants of the first acid-…
Analyser les catastrophes : une approche par les comportements humains
2011
La catastrophe est une forme de crise qui altère profondément un système social soumis à une situation de stress collectif. Ce dernier est confronté à une agression qui surpasse ses capacités d'adaptation induisant une désorganisation sociale et territoriale plus ou moins longue. L'environnement physique, qui influe peu sur les comportements observés en situation normale, contrairement à l'environnement social, impose de nouvelles façons d'agir, de nouveaux modes d'organisation, quelles que soient les échelles considérées. Il s'agit au moment du choc d'assurer sa survie et celle de ses proches (à condition qu'ils ne soient pas trop éloignés spatialement), puis une fois le danger écarté, de …
Coordination chemistry on surfaces through vapor phase processing: smart molecular/graphene heterostructures based on spin-crossover complexes and 2D…
2023
Los compuestos de coordinación están últimamente focalizando la atención de los investigadores en el campo de la nanociencia. Particular interés están generando aquellos compuestos con propiedades magnéticas de cara a su integración a la nanoescala en ramas como la electrónica y/o la espintrónica moleculares. Sin embargo, para su uso real en dispositivos destinados a estas aplicaciones, su procesabilidad es un requisito indispensable. En el marco de esta necesidad, la presente tesis doctoral se ha destinado al estudio del procesado sobre superficies mediante técnicas de fase gas de dos tipos distintos de compuestos de coordinación. Por tanto, el trabajo se ha dividido en dos partes. La prim…
A nucleophilic gold complex.
2019
Solid-state auride salts featuring the negatively charged Au– ion are known to be stable in the presence of alkali metal counterions. While such electron-rich species might be expected to be nucleophilic (in the same manner as I–, for example), their instability in solution means that this has not been verified experimentally. Here we report a two-coordinate gold complex (NON)AlAuPtBu3 (where NON is the chelating tridentate ligand 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) that features a strongly polarized bond, Auδ––Alδ+. This is synthesized by reaction of the potassium aluminyl compound [K{Al(NON)}]2 with tBu3PAuI. Computational studies of the complex, includ…
Anticancer study of heterobimetallic platinum(II)-ruthenium(II) and platinum(II)-rhodium(III) complexes with bridging dithiooxamide ligand
2019
Abstract Three heterobimetallic platinum (II)/ruthenium (II) and platinum (II)/rhodium (III) complexes, A: Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}-[Ru (p-cymene)Cl], R = isoamyl; B: Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}[Rh (phpy)2], R = isoamyl; C: [Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}-[Rh(C5Me5)Cl]], R = benzyl, were prepared from mononuclear complexes 1 and 2, 1: [Pt (H-isoamyl2DTO)2]; 2: [Pt (H-benzyl2DTO)2], DTO = dithiooxamide, by reaction of 1 or 2 with the corresponding chlorido-bridged dimers, [Rh(C5Me5)Cl (μ-Cl)]2, [Ru (p-cymene)Cl (μ-Cl)]2 or [Rh (phpy)2 (μ-Cl)]2, and then evaluated as anticancer agents for the inhibition of the three proteolytic activities of human 20S proteasome, one of the main target …