Search results for " COMPLEXES"
showing 10 items of 818 documents
C−C Cross-Couplings from a Cyclometalated Au(III) C∧ N Complex: Mechanistic Insights and Synthetic Developments
2021
Abstract In recent years, the reactivity of gold complexes was shown to extend well beyond π‐activation and to hold promises to achieve selective cross‐couplings in several C−C and C−E (E=heteroatom) bond forming reactions. Here, with the aim of exploiting new organometallic species for cross‐coupling reactions, we report on the Au(III)‐mediated C(sp2)−C(sp) occurring upon reaction of the cyclometalated complex [Au(CCH2N)Cl2] (1, CCH2N=2‐benzylpyridine) with AgPhCC. The reaction progress has been monitored by NMR spectroscopy, demonstrating the involvement of a number of key intermediates, whose structures have been unambiguously ascertained through 1D and 2D NMR analyses (1H, 13C, 1H‐1H CO…
Organoplatinum(II) Complexes Self-Assemble and Recognize AT-Rich Duplex DNA Sequences
2021
The specific recognition of AT-rich DNA sequences opens up the door to promising diagnostic and/or therapeutic strategies against gene-related diseases. Here, we demonstrate that amphiphilic PtII complexes of the type [Pt(dmba)(N∧N)]NO3 (dmba = N,N-dimethylbenzylamine-κN, κC; N∧N = dpq (3), dppz (4), and dppn (5)) recognize AT-rich oligonucleotides over other types of DNA, RNA, and model proteins. The crystal structure of 4 shows the presence of significant π-stacking interactions and a distorted coordination sphere of the d8 PtII atom. Complex 5, containing the largest π-conjugated ligand, forms supramolecular assemblies at high concentrations under aqueous environment. However, its aggreg…
Photomagnetic properties of an Iron(II) low-spin complex with an unusually long-lived metastable LIESST state
2007
A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long…
Improving diagnostic accuracy of MDCT coronary angiography in patients with mild heart rhythm irregularities using ECG editing
2006
OBJECTIVE. The objective of our study was to compare diagnostic accuracy of MDCT coronary angiography in a population of patients with mild heart rhythm irregularities before and after editing the ECG. SUBJECTS AND METHODS. Thirty-eight patients who underwent MDCT coronary angiography and conventional coronary angiography were enrolled in the study. The inclusion criterion was the presence of mild heart rhythm irregularities (i.e., premature beats; atrial fibrillation; mistriggering; or low heart rate, defined as 40 beats per minute or less) during the scan. All patients underwent MDCT with the following parameters: 16 detectors; collimation, 0.75 mm; gantry rotation time, 375 msec; 120 kV;…
Complexation behaviour of hexadentate ligands possessing N2O4and N2O2S2cores: differential reactivity towards Co(ii), Ni(ii) and Zn(ii) salts and str…
2004
Reactions of divalent metal salts of Co, Ni and Zn with 1,2-di(salicylaldimino-o-phenylthio) ethane (H2L1) and 1,2-di(naphthaldimino-o-phenylthio) ethane (H2L2), having N2O2S2 cores, and 1,2-di(O-salicylaldimino-o-hydroxyphenyl) ethane (H2L3), having a N2O4 core, have been explored. Out of the three ligands and the nine products obtained from the corresponding reactions, two ligands and seven products were crystallographically characterized. However, all the ligands and the products were characterized by analytical and spectral methods. Reaction of H2L1 and H2L2 with Co(II) salts results in oxidative cleavage of the C-S bond to produce a Co(III) product bound to two dissimilar tridentate li…
Structure of mammalian plasma fetuin-B and its mechanism of selective metallopeptidase inhibition
2018
The co-crystal structure of the metallopeptidase astacin with its specific protein inhibitor fetuin-B reveals a novel mechanism of inhibition.
Synthesis, crystal structure and magnetic properties of a new cyanide-bridged mixed-valence copper(I)/copper(II) clathrate
2013
A unique cyanide-bridge mixed-valence CuI/CuII clathrate of formula [CuI2(CN)3][{CuII(tren)}2(μ-CN)](CF3SO3)2 [tren = tris(2-aminoethyl)amine] containing cyanide-bridged [{CuII(tren)}2(μ-CN)]3 + binuclear cations stacked between anionic honeycomb layered copper(I) cyanide networks, was synthesized and structurally characterized by single crystal X-ray diffraction. Variable-temperature magnetic susceptibility studies showed that the cyanide bridge mediates a strong antiferromagnetic interaction between the copper(II) centers (J = − 160 cm− 1, the spin Hamiltonian being defined as H = − JSA⋅SB).
Reinforced cyclam derivatives functionalized on the bridging unit
2016
International audience; A new synthetic method has been developed for the preparation of reinforced cyclams (1,4,8,11-tetraazacyclotetradecane) C-functionalized on the bridging unit, by using a "one pot" reaction starting from the appropriate bis-aminal cyclam intermediate. The high reactivity of quaternized aminal moiety toward nucleophilic agent has been used to elaborate a new class of cross-bridged and side-bridged cyclam derivatives containing cyanide group on the ethylene bridge. Several chelators and corresponding copper(II) complexes have been prepared and characterized by X-ray diffraction. These new constrained polyazamacrocycles are valuable precursors of bifunctional chelating a…
Copper-Assisted Hemiacetal Synthesis: A Cu II Chain Obtained by a One-Step in situ Reaction of Picolinaldehyde
2014
International audience; The 1D polymer complex [Cu2(L)2(SCN)2]n (1 ) has been synthesised in a one‐step in situ reaction of picolinaldehyde with sodium thiocyanate. The complex 1 was characterised by FTIR spectroscopy, UV/Vis spectrophotometry and elemental analysis. The crystal structure of complex 1 shows that chains of dimer complexes are formed with tetra‐ and pentacoordinate copper centres alternately linked by one thiocyanato and two alkoxido bridges. Variable‐temperature magnetic measurements showed a strong antiferromagnetic interaction between the copper centres within the dimer mediated by the two alkoxido bridges with a J value of –374 cm–1, which is in agreement with the DFT‐cal…
Pyrazolium- and 1,2-Cyclopentadiene-Based Ligands as σ-Donors: a Theoretical Study of Electronic Structure and Bonding
2012
A high-level theoretical investigation of 1,2-cyclopentadiene (4) was performed using density functional theory and wave function methods. The results reveal that, in contrast to earlier assumptions, the ground state of this ephemeral “allene” is carbene-like with a small diradical component. Furthermore, the electronic structure and chemistry of 4 are found to parallel that of 1,2,4,6-cycloheptatetraene: both molecules possess a low-lying excited singlet state with a closed-shell carbenic structure, enabling rich coordination chemistry. Energy decomposition analyses conducted for currently unknown metal complexes of 4 as well as those involving stable carbenes based on the pyrazolium frame…