Superbasic alkyl-substituted bisphosphazene proton sponges: a new class of deprotonating matrices for negative ion matrix-assisted ionization/laser desorption mass spectrometry of low molecular weight hardly ionizable analytes.

RATIONALE: Here hardly ionizable and low molecular weight compounds are detected in negative ion mode by using novel superbasic proton sponges based on 1,8-bisphosphazenylnaphthalene (PN) as MALDI matrices. Among the selected proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) has shown the best behaviour as matrix since it allows the direct detection of intact cholesterol without derivatization also in real challenging samples. METHODS: Very weakly acidic compounds such as sterols, steroids, fatty alcohols and saccharides were detected in reflectron negative ion mode by a MALDI TOF/TOF system equipped with a neodymium-doped yttrium lithium fluoride (Nd:YLF) laser (345 nm) with typical mass accuracy of 10 ppm. MS/MS experiments were performed by using ambient air as the collision gas. RESULTS: Contrary to traditional MALDI matrices, superbasic proton sponges allowed the easy deprotonation of an alcohol functional group without a previous chemical derivatization step. Experimental evidence indicates that analyte deprotonation is achieved in the condensed phase, i.e. PN superbasic proton sponges operate according to a recently proposed model named matrix assisted ionization/laser desorption (MAILD). A detection limit of 3 pmol/spot of cholesterol (model compound) with a signal-to-noise ratio ≥ 10 was typically obtained. CONCLUSIONS: For the first time, the usefulness of novel superbasic proton sponges is demonstrated for MALDI detection of hardly ionizable compounds such as sterols, steroids, fatty alcohols and saccharides. The leading candidate TPPN has been successfully applied for negative ion MAILD-MS analysis of cholesterol, fatty acids and phospholipids in egg yolk and brain tissue extracts. Copyright © 2016 John Wiley & Sons, Ltd.

Enhanced lithium transference numbers in ionic liquid electrolytes.

Ion transport processes in mixtures of N-butyl- N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) were characterized by ac impedance spectroscopy and pulsed field gradient NMR. Molar ratios x = n Li-TFSI/( n Li-TFSI + n BMP-TFSI) up to 0.377 could be achieved without crystallization. From the bulk ionic conductivity and the individual diffusion coefficients of cations and anions we calculate the Haven ratio and the apparent lithium transference number. Although the Haven ratio exhibits typical values for ionic liquid electrolytes, the maximal apparent lithium transference number is higher than found in other recent studies on ionic liquid electrolytes containing lithium ions. On the basis of these results we discuss strategies for further improving the lithium transference number of such electrolytes.

The Lewis superacid Al[N(C6F5)2]3 and its higher homolog Ga[N(C6F5)2]3 - structural features, theoretical investigation and reactions of a metal amide with higher fluoride ion affinity than SbF5.

Herein we present the synthesis of the two Lewis acids Al[N(C6F5)2]3 (ALTA) and Ga[N(C6F5)2]3 (GATA) via salt elimination reactions. The metal complexes were characterized by NMR-spectroscopic methods and X-ray diffraction analysis revealing the stabilization of the highly Lewis acidic metal centers by secondary metal-fluorine contacts. The Lewis acidic properties of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 are demonstrated by reactions with Lewis bases resulting in the formation of metallates accompanied by crucial structural changes. The two metallates [Cs(Tol)3]+[FAl(N(C6F5)2)3]- and [AsPh4]+[ClGa(N(C6F5)2)3]- contain interesting weakly coordinating anions. The reaction of Al[N(C6F5)2]3 with trityl fluoride yielded [CPh3]+[FAl(N(C6F5)2)3]- which could find application in the activation of metallocene polymerization catalysts. The qualitative Lewis acidity of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 was investigated by means of competition experiments for chloride ions in solution. DFT calculations yielded fluoride ion affinities in the gas phase (FIA) of 555 kJ mol-1 for Al[N(C6F5)2]3 and 472 kJ mol-1 for Ga[N(C6F5)2]3. Thus, Al[N(C6F5)2]3 can be considered a Lewis superacid with a fluoride affinity higher than SbF5 (493 kJ mol-1) whereas the FIA of the corresponding gallium complex is slightly below the threshold to Lewis superacidity.

Formazanido complexes of heavier group 13 elements aluminium, gallium, and indium.

The preparation, molecular structures and physical properties of novel heavy group 13 metal formazanido complexes are described. The trimethyl derivatives MMe3 (M = Al, Ga, In) react with 1,3,5-triphenylformazan (Htpf) in a 1 : 1 ratio to give methane and metallacycles of the type [M(tpf)Me2]. While [Al(tpf)Me2] and [Ga(tpf)Me2] are mononuclear compounds with six-membered rings and coordination number 4 in solution and in the crystalline state, indium derivative [In(tpf)Me2] forms oligomers in non-coordinating solvents according to NMR studies, these are probably N-bridged dimers with coordination number 5 at indium. The oligomer is cleaved by addition of one equivalent of pyridine or 4-dimethylaminopyridine (DMAP). The complexes [M(tpf)Me2] (M = Al, Ga) and [In(tpf)Me2(DMAP)] are characterized by XRD analyses. They are unique examples of main group metal formazane ring systems of the third and higher periods. The UV-Vis solution spectra of the neutral ligand Htpf and its metallated compounds [M(tpf)Me2] (M = Al, Ga, In) are discussed.

Access to pure and highly volatile hydrochalcogenide ionic liquids.

The reaction of methylcarbonate ionic liquids with H2S or H2Se offers a highly selective synthesis of analytically pure, well-defined and soluble hydrosulphide and hydroselenide organic salts of general interest. Among them, imidazolium hydrochalcogenides show an astonishingly high volatility for cation-aprotic ILs, which allows their quantitative sublimation below 100 °C/10(-2) mbar and actually results in ionic single crystal growth from the gas phase. Vaporisation and decomposition characteristics were investigated by isothermal TGA measurements and DFT calculations.

In search of catalytically active species in the surfactant-mediated biphasic alkene epoxidation with Mimoun-type complexes.

[figure: see text] A biphasic protocol for the catalytic olefin epoxidation with Mimoun-type complexes [MoO(O2)2(OPR3)] (1) was recently patented by BASF. Density-functional calculations have been carried out to identify potentially active species in addition to the parent complex 1. It has been found that the (mu 2,eta 1:eta 2-O2)-bridged dimer [MoO(O2)2(OPR3)]2 is significantly less reactive than the monomer. The calculations show that the parent complex is strongly activated by protons coordinating with the peroxo functionalities.

Mediastinal teratoma presenting as a rapidly enlarging paracardial mass.

Mediastinal teratomas are usually found incidentally at chest x-ray. It is the purpose of this communication to describe a case of benign anterior mediastinal teratoma, which presented as a rapidly expanding paracardial mass in a young man.

Copper complexes of novel superbasic peralkylguanidine derivatives of tris(2-aminoethyl)amine as constraint geometry ligands.

The coordination chemistry of copper(I) and copper(II) ions with novel tripodal peralkylguanidine derivatives of the tris(2-aminoethyl)amine (tren) backbone TMG(3)tren (tetramethylguanidino-tren) N[CH(2)CH(2)N=C(NMe(2))(2)](3) (1) and cyclic DMPG(3)tren (dimethylpropyleneguanidino-tren) N[CH(2)CH(2)N=C[NMe(CH(2))(3)NMe]](3) (2) is reported. These sterically demanding ligands form complexes of constraint trigonal geometry. Their superbasic character with estimated pK(BH)+ values 6 orders of magnitude higher than that of the known Me(6)tren and their softer N-donor character compared to tert-amine ligands stabilize cationic mononuclear Cu(I) and Cu(II) ions by delocalization of charge into the guanidine functionalities. The crystal structures and spectroscopic features of two cationic copper(I) complexes with an uncommon trigonal-pyramidal [N(4)Cu](+) coordination sphere and a sterically protected open coordination site and of two cationic copper(II) complexes with the characteristic trigonal-bipyramidal coordination geometry [N(4)CuCl](+) and [N(5)Cu](2+) are reported.

Theoretical studies of molybdenum peroxo complexes [MoOn(O2)3-n(OPH3)] as catalysts for olefin epoxidation.

The equilibrium geometries of the molybdenum oxo/peroxo compounds MoOn(O2)3-n and the related complexes [MoOn(O2)3-n(OPH3)] and [MoOn(O2)3-n(OPH3)(H2O)] (n = 0-3) have been calculated using gradient-corrected density-functional theory at the B3LYP level. The structures of the peroxo complexes with ethylene ligands [MoOn(O2)3-n(C2H4)] and [MoOn(O2)3-n(OPH3)(C2H4)] (n = 1, 2) where ethylene is directly bonded to the metal have also been optimized. Calculations of the metal-ligand bond-dissociation energies show that the OPH3 ligand in [MoOn(O2)3-n(OPH3)] is much more strongly bound than the ethylene ligand in [MoOn(O2)3-n(C2H4)]. This makes the substitution of phosphane oxide by olefins in the epoxidation reaction unlikely. An energy-minimum structure is found for [MoO(O2)2(OPH3)(C2H4)], for which the dissociation of C2H4 is exothermic with D0 = -5.2 kcal/mol. The reaction energies for the perhydrolysis of the oxo complexes with H2O2 and the epoxidation of ethylene by the peroxo complexes have also been calculated. The peculiar stability of the diperoxo complex [MoO(O2)2(OPH3)(H2O)] can be explained with the reaction energies for the perhydrolysis of [MoOn(O2)3-n(OPH3)(H2O)]. The first perhydrolysis step yielding the monoperoxo complex is less exothermic than the second perhydrolysis reaction, but the further reaction with H2O2 yielding the unknown triperoxo complex is clearly endothermic. CDA analysis of the metal-ethylene bond shows that the binding interactions are mainly caused by charge donation from the ligand to the metal.