9/24 News More research is needed about Dichloro(pentamethylcyclopentadienyl)iridium(III) dimer

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The crystal structure of 1,8,10,17-tetraazapentacyclo[8.8.1.1 8,17.02,7.011,16]icosane (1) has been determined by single crystal X-ray diffraction analysis. The title compound crystallized in space group Fddd. The asymmetric unit is modeled as a 45:55 disorder between the R,R,R,R and S,S,S,S forms of the molecule. The structure exhibits a ‘twisted lawn chair’ conformation with both nitrogen atoms attached to the cyclohexane ring adopting the equatorial positions. In each molecule all chiral centers are of the same configuration; however both the R,R,R,R and S,S,S,S conformations are present in the unit cell and are related by a center of inversion. The crystal structure of 1 is compared with the structure of the tetraazadodecane (5).

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Sep-21 News The important role of Dichloro(pentamethylcyclopentadienyl)iridium(III) dimer

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A library of chiral zinc complexes formed in situ by the combination of achiral and racemic diimines with 3,3?-di(3,5-ditrifluoromethylphenyl)- BINOL and diethylzinc were evaluated in the asymmetric addition of diethylzinc to N-acylimines. In the presence of 10 mol % of chiral ligand 4 and racemic diimine 5, high enantioselectivities of up to 97% ee and yields of up to 96% were achieved for a wide range of aromatic imines in dichloromethane at -30C.

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24-Sep-21 News Discovery of 2-Methylcyclohexane-1,3-dione

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Copper(i) (±)-N,N?-bis(2,4,6-trimethylbenzylidene)-1,2- diaminocyclohexane reacts with either ethene or butadiene to give the corresponding alkene complexes. In each case crystallographic studies show that the alkene coordinates in an eta2 fashion. In the butadiene complex a dimer is formed where the butadiene bridges two copper complexes. Variable temperature NMR spectroscopy of the ethene adduct demonstrates fluxional behaviour, which is attributed to the rotation of the coordinated ethene relative to the complex, DeltaG?255 = 50 ± 2 kJ mol-1.

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24-Sep News Extended knowledge of Bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate

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Contrast-enhanced computed tomography (CT) and magnetic resonance imaging (MRI) are routinely used to diagnose soft tissue and vascular abnormalities. However, safety concerns limit the use of iodinated and gadolinium (Gd)-based CT and MRI contrast media in renally compromised patients. With an estimated 14% of the US population suffering from chronic kidney disease (CKD), contrast media compatible with renal impairment is sorely needed. We present the new manganese(II) complex [Mn(PyC3A)(H2O)]- as a Gd alternative. [Mn(PyC3A)(H2O)]- is among the most stable Mn(II) complexes at pH 7.4 (log KML = 11.40). In the presence of 25 mol equiv of Zn at pH 6.0, 37 C, [Mn(PyC3A)(H2O)]- is 20-fold more resistant to dissociation than [Gd(DTPA)(H2O)]2-. Relaxivity of [Mn(PyC3A)(H2O)]- in blood plasma is comparable to commercial Gd contrast agents. Biodistribution analysis confirms that [Mn(PyC3A)(H2O)]- clears via a mixed renal/hepatobiliary pathway with >99% elimination by 24 h. [Mn(PyC3A)(H2O)]- was modified to form a bifunctional chelator and 4 chelates were conjugated to a fibrin-specific peptide to give Mn-FBP. Mn-FBP binds the soluble fibrin fragment DD(E) with Kd = 110 nM. Per Mn relaxivity of Mn-FBP is 4-fold greater than [Mn(PyC3A)(H2O)]- and increases 60% in the presence of fibrin, consistent with binding. Mn-FBP provided equivalent thrombus enhancement to the state of the art Gd analogue, EP-2104R, in a rat model of arterial thrombosis. Mn metabolite analysis reveals no evidence of dechelation and the probe was >99% eliminated after 24 h. [Mn(PyC3A)(H2O)]- is a lead development candidate for an imaging probe that is compatible with renally compromised patients.

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Sep-21 News New explortion of Bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate

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With the aim of expanding the structure-activity relationship investigation, the series of Ru(ii) half sandwich coordination compounds of the type [Ru([9]aneS3)(chel)(L)]n+ previously described by us (where [9]aneS3 is the neutral face-capping ligand 1,4,7-trithiacyclononane, chel is a neutral or anonic chelating ligand, L = Cl- or dmso-S, n = 0-2) was extended to 1,4,7-triazacyclononane ([9]aneN3). In addition, new neutral N-N, and anionic N-O and O-O chelating ligands, i.e. dach (trans-1,2- diaminocyclohexane), pic- (picolinate), and acac- (acetylacetonate), were investigated in combination with both [9]aneS3 and [9]aneN3. Overall, ten new half-sandwich complexes were prepared and fully characterized and their chemical behaviour in aqueous solution was established. The single-crystal X-ray structures of eight of them, including the versatile precursor [Ru([9]aneN3)(dmso-S)2Cl]Cl (9), were also determined. The results of in vitro antiproliferative tests performed on selected compounds against MDA-MB-231 human mammary carcinoma cells confirmed that, in this series, only compounds that hydrolyse the monodentate ligand at a reasonable rate show moderate activity, provided that the chelate ligand is a hydrogen bond donor.

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9/23 News Discovery of cis-Cyclohexane-1,2-diamine

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Cobalt(III) complexes with N-(aminoalkyl)salicylamide dianions, Ln 2- (n = 14), have been prepared and their molecular and crystal structures have been determined. The geometric (mer- or fac-) selectivity of [Co(Ln)2]- complexes was dependent on the number of the amineamidato chelate ring member. Intermolecular homochiral hydrogen-bonds and solvatochromic behavior of the complexes were also observed.

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23-Sep-21 News A new application about cis-Cyclohexane-1,2-diamine

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The series of nickel(II) and copper(II) complexes (3a-f) bearing tetradentate [ONNO] beta-ketoiminato ligands, N,N?-bis(2-benzoyl-3- oxobutylidene)-o-phenylenediamine 2a, N,N?-bis(2-benzoyl-3-oxobutylidene)- ethylenediamine 2b, N,N?-bis(2-benzoyl-3-oxobutylidene)-trans-1,2- cyclohexanediamine 2c, have been synthesized and characterized. X-ray crystal structures of complexes 3a-c and 3e-f reveal that each central metal adopts an almost square planar coordination geometry. Upon activation with methylaluminoxane (MAO), the nickel(II) complexes 3a-c display high catalytic activities for the vinyl polymerization of norbornene (NB), yielding high molecular weights of the polynorbornene (PNB), especially the complex 3b (24.46 × 105 gPNB/molNi h). While copper(II) complexes 3d-f only traces of PNB are generated. The catalytic system 3b/MAO is chosen for further investigations under various polymerization parameters.

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09/23/21 News Top Picks: new discover of cis-Cyclohexane-1,2-diamine

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6Li and 15N NMR spectroscopic studies of lithium diisopropylamide ([6Li]LDA and [6Li,15N]LDA) in toluene/pentane solutions containing a variety of mono- and polydentate ligands are reported. LDA forms exclusively dimers in the presence of n-BuOMe, Et2O, t-BuOMe, THF, 2- methyltetrahydrofuran, 2,2-dimethyltetrahydrofuran, tetrahydropyran, dimethoxyethane, N,N,N’,N’-tetramethylethylenediamine, and MeOCH2CH2NR2 (NR2 = NMe2, NEt2, pyrrolidino). Addition of 1,2-dipyrrolidinoethane and (2-pyrrolidinoethyl)dimethylamine provides monomer-dimer mixtures. Treatment of LDA with trans-N,N,N’,N’-tetramethylcyclohexanediamine (TMCDA) or trans- 1-(dimethyl-amino)-2-isopropoxycyclohexane in hydrocarbons afford exclusively monomers. Sparteine binds only reluctantly, giving a mixture of unsolvated oligomers and monomer. Competitions of the ethereal ligands vs TMCDA afford binding constants and associated free energies for dimer solvation which are correlated with those obtained previously for lithium hexamethyldisilazide.

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22-Sep News The important role of cis-Cyclohexane-1,2-diamine

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In this study, the Schiff base ligand trans-N,N?-bis[(2,4-dichlorophenyl) methylidene] cyclohexane-1,2-diamine (L) and its copper(II), nickel(II) and palladium(II) transition metal complexes were prepared and characterized by the analytical and spectroscopic methods. The 1H(13C) NMR spectra of the ligand and its diamagnetic complexes were recorded in DMSO-d6 solvent and obtained data confirm that the nitrogen atoms of the imine groups coordinated to the metal ions. Electrochemical properties of the ligand and its metal complexes were investigated in the DMF solvent at the 100 and 250 mV s-1 scan rates. The ligand and metal complexes showed both reversible and irreversible processes at these scan rates. The single crystal of the ligand (L) was obtained from MeOH solution, and its crystal structure was determined by X-ray diffraction. The C-H…Cl hydrogen bonding interactions in the molecule were seen which increase the stability of the crystal structure. The antimicrobial activity studies of the ligand and its metal complexes were carried out by using the various bacteria and fungi.

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22-Sep News Final Thoughts on Chemistry for cis-Cyclohexane-1,2-diamine

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Reaction of Co(CH3COO)2·4H2O, KTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) with the racemic or chiral H 2salency (N,N?-bis(salicylidene)-1,2-cyclohexanediamine) ligand afforded three Co(iii) complexes K[Co(salency)(CN)2]·CH 3OH (1), K[Co(S,S-salency)(CN)2]·H2O (1S) and K[Co(R,R-salency)(CN)2]·CH3OH (1R), which have been fully characterized. The cyanide groups in these three complexes are generated from the in situ decomposition of the radical anion of TCNQ with the participation of cobalt(ii). Single-crystal X-ray diffraction analysis reveals that complex 1 exhibits an infinite double stair-like chain structure. However, the chiral complexes 1S and 1R show chain structures consisting of two independent sub-chains. All of these chains are bridged by the K+ ions, with the cyanides interacting with K+ in the end-on and unusual side-on pi-type mode. Second-order nonlinear optical effect studies in the solid state revealed that 1S and 1R are SHG active. The Royal Society of Chemistry.

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