Solid State Structures and Solution Dynamics of Unsolvated and Diethyl Ether Solvated Dilithium N,N'-Bis(trimethylsilyl)ethylenediamide Complexes

The lithiation of N,N'-bis(trimethylsilyl)ethylenediamine, 1, by 2 equiv of methyllithium in diethyl ether yields the dimeric diethyl ether adduct [{Li[N(SiMe(3))CH(2)CH(2)NSiMe(3)]Li.OEt(2)}(2)], 2. Recrystallization of 2 from benzene gives quantitatively the unsolvated trimer [{Li[N(SiMe(3))CH(2)CH(2)NSiMe(3)]Li}(3)], 3. The solution dynamics of 2 and 3 in toluene have been investigated using variable temperature multinuclear NMR spectroscopy. In solution, 2 is undergoing a rapid exchange process involving an equilibrium between unsolvated and diethyl ether solvated dimers, whereas compound 3 exists in a temperature dependent equilibrium of dimeric and trimeric species, of which the trimer is fluxional and exchanges inequivalent ligands by an intramolecular distortion of the Li(6)N(6) cage structure. Crystals of 2 are monoclinic, of space group P2(1)/n (No. 14), with a = 10.692(9) ?, b = 16.192(2) ?, c = 24.04(4) ?, beta = 101.16(5) degrees, V = 4083(8) ?(3), and Z = 4. Crystals of 3 are trigonal, of space group R&thremacr;m(No. 166), a = 17.765(1) ?, c = 13.394(1) ?, V = 3660.5(5) ?(3), Z = 3.     

Recent advances in solventless organic reactions: towards benign synthesis with remarkable versatility

A paradigm shift away from using solvents in organic synthesis as solventless reactions can lead to improved outcomes, and more benign synthetic procedures, in for example aldol condensation reactions, sequential aldol and Michael addition reactions en route to Kr?hnke type pyridines, reactions leading to 3-carboxycoumarins, benzylidenes, 4-aryl-1,4-dihydropyridines and 2-aryl-1,2,3,4-tetrahydroquinazolines, and oligomerisation reactions for the synthesis of cavitands; kinetic considerations for the reaction of two solids can only be explained if a eutectic melt is formed during the reaction.     

Lanthanide crown ether complexes of p-sulfonatocalix[5]arene

Two types of arrays are formed in water involving aza-crown ethers, p-sulfonatocalix[5]arene and europium(III) ions. One is a co-ordination polymer connecting calixarenes, sodium ions and lanthanide ions based on "ferris wheel" moieties incorporating aza-18-crown-6 and sodium ions. The second structure is a host-guest arrangement with di-protonated diaza-18-crown-6 in the cavity of the calixarenes as part of secondary coordination spheres of aquated europium(iii) ions.     

Observation of the Q(3/2) Λ-doublet transitions for X2Π3/2 OD in helium nanodroplets

The deuteroxyl radical (OD) has been isolated in superfluid helium nanodroplets and characterised by infrared depletion spectroscopy. Two resolved Q(3/2) lines are observed, with a separation that is 4.88 (10) times larger than in the gas phase. This is similar to that previously reported for He-solvated OH (5.30 (2)), for which it was shown that the splitting could be reproduced by a model that assumes a small parity dependence of the rotor's effective moment of inertia [P.L. Raston, T. Liang, and G.E. Douberly, J. Phys. Chem. A (2013). DOI:10.1021/jp312335q]. With this model, the OD Λ-doublet splitting in liquid He is reproduced with B^e and B^f rotational constants that differ by ≈0.24%.     

Vortex fluidic promoted Diels–Alder reactions in an aqueous medium

‘Soft energy’ provided within a thin film microfluidic platform, namely a vortex fluidic device (VFD), is effective in accelerating and promoting Diels–Alder reactions in the absence of any catalyst. Diels–Alder cycloadducts generated from different 9-substituted anthracenes and N-maleimides are formed in high yield in an aqueous medium using the confined mode of operation of the VFD.     

Development and validation of a LC/TOF MS method for the determination of carboplatin and paclitaxel in nanovesicles

Carboplatin and paclitaxel co-loaded nanovesicles (CPT-PTX-CLV), a novel intravenous formulation void of cremophor EL, may have significant advantages over conventional carboplatin and paclitaxel formulations with respect to tumor targeting, sustained drug release, reduced toxicity, and synergistic efficacy profiles. The aim of this study was to develop and validate a rapid, specific, sensitive, and reliable liquid chromatography–time of flight–mass spectrometry (LC/TOF MS)-based bioanalytical method for the simultaneous quantification of CPT and PTX in a fetal bovine serum (FBS) vehicle containing the dispersed nanovesicles. The analytes were extracted from FBS by simple protein precipitation, with subsequent separation of CPT and PTX on a Waters HPLC SunFire C₁₈ column at a flow rate of 0.25 ml/min using gradient elution mode. The total analytical time was only 12 min. Detection and quantitation was performed by electrospray ionization (ESI) in the positive ionization mode with selective ion monitoring (SIM) at m/z 310.0152 for CPT and 876.3224 for PTX. The calibration curves were linear over the concentration range of 10–4,000 ng/ml for CPT and 5–2,000 ng/ml for PTX (r ² ?>?0.99), with the respective lower limit of quantification (LLOQ) at 10 and 5 ng/ml. The intra- and inter-day precision and accuracy of analysis of the quality control samples at low, medium, and high concentration levels were ≤13.6 % relative standard deviation (RSD) and ≤14.6 % relative errors (RE). The rapid, sensitive, and reproducible LC/TOF MS method may be used to support preclinical and clinical pharmacological studies of the CPT-PTX-CLV administered by injection in animal and human cancer models.

Capture of di-protonated [2.2.2]cryptand in the cavity of two p-sulfonated calixarenes as part of 2-D bi-layer lanthanide coordination polymers

Treating p-sulfonatocalix[4]arene with lanthanide ions, Ln3+ (Ln = Ce, Nd, Sm and Eu), in the presence of [2.2.2]cryptand results in a 2-D bi-layer coordination polymer with axially elongated diprotonated cryptand in the cavity of two p-sulfonatocalix[4]arenes.     

Ni(II) N4-macrocycle grafted crown ether: caesium cobalt(III) bis(dicarbollide) coordination polymer

A mixture of a Ni(TMTAA) grafted crown ether and Cs[Co(C2B9H11)2] in toluene-CH2Cl2 affords a 1:1 complex, comprised of layers of infinite two-dimensional polymeric arrays separated by layers of the cobalticarborane anion which themselves form two B-H...Cs+ hydrogen interactions.     

Direct preparation of monoarylidene derivatives of aldehydes and enolizable ketones with DIMCARB

[reaction: see text] Aryl alpha,beta-unsaturated ketones and aldehydes were synthesized, in moderate to excellent yields, with use of dimethylammonium dimethyl carbamate (DIMCARB) as a recyclable reaction medium and as a catalyst.