Three manganese complexes of anionic N4-donor Schiff-base macrocycles: 1 monomeric Mn(II) and Mn(III), and dimeric Mn(IV)

Three manganese macrocyclic complexes of two anionic N4-donor [1+1] Schiff-base macrocycles that differ in ring size (14 vs 16 membered), HLEt and HLPr (obtained from condensation of diphenylamine-2,2’-dicarboxaldehyde and either diethylenetriamine or dipropylenetriamine), are reported. Specifically, a pair of monomeric complexes MnIILEt(NCS)(H2O) and [MnIIILPr(NCS)2]•0.5H2O, plus a dimeric complex [MnIV2LEt2(O)2](ClO4)2•3DMF have been synthesised and characterised. Single crystal structure determinations on [MnIIILPr(NCS)2]•0.5H2O and [MnIV2LEt2(O)2](ClO4)2•3DMF revealed octahedral manganese centres in both cases: N6-coordinated Jahn-Teller distorted Mn(III) in the former and a pair of N4O2-coordinated Mn(IV) in the latter. UV-vis, IR and EPR spectroscopy as well as magnetic measurements are reported. These macrocyclic complexes feature a simple and original design, and could find future uses as models for manganese catalase or as building blocks for the assembly of larger supramolecular architectures

An inverted-sandwich diuranium μ-η5:η5-cyclo-P5 complex supported by U-P5 δ-bonding

Reaction of [U(TrenTIPS)] [1, TrenTIPS=N(CH2CH2NSiiPr3)3] with 0.25 equivalents of P4 reproducibly affords the unprecedented actinide inverted sandwich cyclo-P5 complex [{U(TrenTIPS)}2(μ-η5:η5-cyclo-P5)] (2). All prior examples of cyclo-P5 are stabilized by d-block metals, so 2 shows that cyclo-P5 does not require d-block ions to be prepared. Although cyclo-P5 is isolobal to cyclopentadienyl, which usually bonds to metals via σ- and π-interactions with minimal δ-bonding, theoretical calculations suggest the principal bonding in the U(P5)U unit is polarized δ-bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P5 unit to give a cyclo-P5 charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P5 compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium δ-symmetry 5f orbitals

Synthesis and characterization of an f‑block terminal parent imido [U=NH] complex: a masked uranium(IV) nitride

Deprotonation of [U(TrenTIPS)(NH2)] (1) [TrenTIPS = N(CH2CH2NSiPri3)3] with organoalkali metal reagents MR (M = Li, R = But; M = Na−Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U-(TrenTIPS)(μ-N[H]M)}2] [M = L −Cs (2a−e)]. Treatmentof 2c (M = K) with 2 equiv of 15 crown-5 ether (15C5) afforded the uranium terminal parent imido complex [U(TrenTIPS)(NH)][K(15C5)2] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium−imido linkage was found to be essentially linear, and theoretical calculations suggested σ2π4 polarized U−N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(TrenTIPS)(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium−nitride complex [U(TrenTIPS)(N)] (5); this reaction is a new way to prepare the terminal uranium−nitride linkage and was calculated to be exothermic by −3.25 kcal mol−1

Synthesis, structure, and cytotoxicity studies of oxidovanadium(IV and V) complexes bearing chelating phenolates

The interaction of [VO(acac)2] with 2,6-bis(hydroxymethyl)-4-methylphenol (L1H3) or 6,6/-methylenebis(4-tert-butyl-2-(hydroxymethyl)phenol) (L2H4) in refluxing toluene afforded, following work-up in ethanol, the complexes [VOL1]2 (1) and {[VO(acac)(HOEt)](VO)L2]}2 (2), respectively. Use of 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]benzoic acid (L3H2) or 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]benzosulfonic acid (L4H2) with [VOCl3] in refluxing acetonitrile, followed by methanol and THF work-up, afforded the complexes [Et3NH][VO(OMe)L3]2 (3) and [Et3NH][VO(OMe)L4]2 (4), respectively. The interaction of [VOSO4] and L3H2 in refluxing acetonitrile afforded, with extraction into methanol, the complex [VO(OMe)L3]2 (5). The molecular structures of 2, 3 and 5 have been determined; the structure of 1 has been reported previously. The complexes in this study have been determined to be of low toxicity using in vitro cell assays with 50% cytotoxicity values (CC50) values in the range 56 – 126 µM

Isolation of elusive HAsAsH in a crystalline diuranium(IV) complex

The HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π*-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form

Exquisite sensitivity of the ligand field to solvation and donor polarisability in coordinatively saturated lanthanide complexes

Crystallographic, emission and NMR studies of a series of C3-symmetric, nine-coordinate substituted pyridyl triazacyclononane Yb(III) and Eu(III) complexes reveal the impact of local solvation and ligand dipolar polarisability on ligand field strength, leading to dramatic variations in pseudocontact NMR shifts and emission spectral profiles, giving new guidance for responsive NMR and spectral probe design

Reversible adsorption and confinement of nitrogen dioxide within a robust porous metal-organic framework

Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental and health problems. We report reversible adsorption of NO2 in a robust metal–organic framework. Under ambient conditions, MFM-300(Al) exhibits a reversible NO2 isotherm uptake of 14.1 mmol g−1, and, more importantly, exceptional selective removal of low-concentration NO2 (5,000 to <1 ppm) from gas mixtures. Complementary experiments reveal five types of supramolecular interaction that cooperatively bind both NO2 and N2O4 molecules within MFM-300(Al). We find that the in situ equilibrium 2NO2 ↔ N2O4 within the pores is pressure-independent, whereas ex situ this equilibrium is an exemplary pressure-dependent first-order process. The coexistence of helical monomer–dimer chains of NO2 in MFM-300(Al) could provide a foundation for the fundamental understanding of the chemical properties of guest molecules within porous hosts. This work may pave the way for the development of future capture and conversion technologies

Catalytic decomposition of NO2 over a copper-decorated metal-organic framework by non-thermal plasma

Efficient catalytic conversion of NO2 to non-harmful species remains an important target for research. State-of-the-art deNOx processes are based upon ammonia (NH3)-assisted selective catalytic reduction (NH3-SCR) over Cu-exchanged zeolites at elevated temperatures. Here, we describe a highly efficient non-thermal plasma (NTP) deNOx process catalyzed by a Cu-embedded metal-organic framework, Cu/MFM-300(Al), at room temperature. Under NTP activation at 25°C, Cu/MFM-300(Al) enables direct decomposition of NO2 into N2, NO, N2O, and O2 without the use of NH3 or other reducing agents. NO2 conversion of 96% with a N2 selectivity of 82% at a turnover frequency of 2.9 h−1 is achieved, comparable to leading NH3-SCR catalysts that use NH3 operating at 250°C–550°C. The mechanism for the rate-determining step (NO→N2) is elucidated by in operando diffuse reflectance infrared Fourier transform spectroscopy, and electron paramagnetic resonance spectroscopy confirms the formation of Cu2+⋯NO nitrosylic adducts on Cu/MFM-300(Al), which facilitates NO dissociation and results in the notable N2 selectivity

Structure and electronic properties of an asymmetric thiolate-bridged binuclear complex: a model for the active site of acetyl CoA synthase

The asymmetric binuclear complex [(dppe)Ni(μ-‘S, S’)Ni(L)](PF6)2 [L = (N, N′-diethyl-3,7-diazanonane-1,9-dithiolato)2−] shows a reversible one-electron reduction to afford a mixed-valent Ni(II)·Ni(I) species; the reduced complex has been characterised by EPR spectroscopy and mimics the redox active Nip site in the active A-cluster of acetyl coenzyme A synthase