Cyclopropanation Using Electrons Derived from Hydrogen: Reaction of Alkenes and Hydrogen without Hydrogenation.

Have you ever imagined reactions of alkenes with hydrogen that result in anything other than hydrogenation or hydrogenative C-C coupling? We have long sought to develop not only hydrogenation catalysts that activate H2 as hydride ions but also electron transfer catalysts that activate H2 as a direct electron donor. Here, we report the reductive cyclopropanation of alkenes using an iridium electron storage catalyst with H2 as the electron source without releasing metal waste from the reductant. We discuss the catalytic mechanism with selectivity to give the trans-isomer. These findings are based on the isolation of three complexes and density functional theory calculations.

Serological analysis of severe acute respiratory syndrome coronavirus 2 infection in children with Kawasaki disease.

Multisystem inflammatory syndrome in children (MIS-C) was reported as a severe complication of coronavirus disease 2019; an infection with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), and was suggested to be associated with Kawasaki disease (KD) in terms of severe systemic inflammation and mucocutaneous symptoms. Because severe gastrointestinal symptoms and systemic shock are more frequently observed with MIS-C, patients with mild MIS-C might have been diagnosed with KD. In this study, titers of IgG antibodies against the SARS-CoV-2 S (S-IgG) and N proteins (N-IgG) were measured in 99 serum samples collected from patients with KD treated between January 2020 and December 2021 to evaluate the relationship between KD and SARS-CoV-2 infection. S-IgG were detected in only one patient out of 99 patients. This patient had coronavirus disease 2019 (COVID-19) 10 months before KD onset, and was unlikely MIS-C. According to characters of S-IgG and N-IgG, the patients was unlikely infected with SARS-CoV-2 just before the onset of KD. In addition to this study, the 26th Nationwide Survey and previous studies showed an association between KD and SARS-CoV-2 to be unlikely. In conclusion, SARS-CoV-2 infection was not observed in patients with KD until Delta predominance in Japan by the method of detecting SARS-CoV-2 IgG.

Storing electrons from H2 for transfer to CO2, all at room temperature.

We present an Ir complex that extracts electrons from H2 at room temperature and stores them as a H2-derived energy carrier (H2EC) at room temperature. Furthermore, we demonstrate that this complex reduces CO2 to a metal-CO22- species at room temperature, and present the first electrospray ionisation mass spectrum for this compound.

Single-Step Synthesis of NiI from NiII with H2.

Chemists have long sought to regulate the reactivity of H2 , to yield hydride ions, hydrogen atoms, or electrons on demand. One source of inspiration for achieving this control is [NiFe]hydrogenase ([NiFe]H2 ase), which reacts with H2 to form various hydrogen active species such as NiIII hydride species, NiII hydride species, and NiI low-valent species. Chemists have attempted to synthesize these hydrogen active species not only as models for the active species of [NiFe]H2 ase, but also as electron transfer catalysts. However, the synthesis of NiI complex directly from H2 has not been reported. This paper reports the first example of a single-step synthesis of a NiI complex, via reaction of a NiII complex with H2 , stable for over 3 months at room temperature and we further demonstrate a reductive coupling of acridinium ions as part of a reaction cycle.

A series of (E)-1,2-diaryldigermenes incorporating bulky Eind groups: structural characteristics and absorption properties.

A series of (E)-1,2-diaryldigermenes, (Eind)ArGeGeAr(Eind) [Ar = phenyl (2), thiophen-2-yl (3), 9,9-dimethyl-2-fluorenyl (4) and 2,2'-bithiophen-5-yl (5)], supported by the fused-ring bulky 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl (Eind) groups, have been obtained as yellow-orange to red crystalline solids by the reaction of 1,2-dibromodigermene, (Eind)BrGeGeBr(Eind) (1), with ArLi. In the crystals of 2-5, the digermene cores show a flexible nature adopting a trans-bent geometry with the trans-bent angles (θ) between the Ge-Ge vector and the CEind-Ge-CAr plane of 34.04(12)° (2), 38.3(3)° and 38.8(3)° (3), 33.69(12)° (4) and 39.30(13)° (5). In the UV-vis spectra, strong π-π* absorptions have been observed with an absorption maximum at 451 nm (ε = 1.3 × 104) (2), 455 nm (ε = 9.7 × 103) (3), 480 nm (ε = 1.3 × 104) (4) and 497 nm (ε = 1.4 × 104) (5), retaining the GeGe double bond in solution. The absorption data and DFT calculations provide evidence for the intrinsic π-conjugation between the GeGe chromophore and aromatic rings involving the narrowing of the HOMO-LUMO gaps (ΔE) with the extension of the carbon π-electron systems.

Unusual motion of the n-methoxypropyl moiety observed in the photochromic crystals of an organorhodium dithionite complex with n-methoxypropyltetramethylcyclopentadienyl ligands.

The crystalline-state photochromism of a new organorhodium dinuclear complex having n-methoxypropyltetramethylcyclopentadienyl (η5-C5Me4n-C3H6OCH3) and photoresponsive dithionite (µ-O2SSO2) ligands was investigated directly by performing single-crystal X-ray diffraction experiments; a reversible conformational change of the n-methoxypropyl moiety was intriguingly observed during the course of a thermal back-reaction.

C-H Arylation of Benzene with Aryl Halides using H2 and a Water-Soluble Rh-Based Electron Storage Catalyst.

This paper reports the first example of C-H arylation of benzene under mild conditions, using H2 as an electron source {turnover numbers (TONs)=0.7-2.0 for 24 h}. The reaction depends on a Rh-based electron storage catalyst, and proceeds at room temperature and in aqueous solution. Furthermore, the H2 is inactive during the radical transfer step, greatly reducing unwanted side reactions.

Reductive C(sp3)-C(sp3) homo-coupling of benzyl or allyl halides with H2 using a water-soluble electron storage catalyst.

This paper reports the first example of a reductive C(sp3)-C(sp3) homo-coupling of benzyl/allyl halides in aqueous solution by using H2 as an electron source {turnover numbers (TONs) = 0.5-2.3 for 12 h}. This homo-coupling reaction, promoted by visible light, is catalysed by a water-soluble electron storage catalyst (ESC). The reaction mechanism, and four requirements to make it possible, are also described.

A non-linear phenomenon observed in the photochromic crystals of a rhodium dithionite complex with n-propyl moieties.

Crystalline-state photochromism of a rhodium dithionite complex with n-propyl moieties was studied directly by performing single crystal X-ray diffraction experiments; a non-linear relationship between the degree of the conformational change of the n-propyl moiety and the degree of the photochromic reaction of the dithionite group (µ-O2SSO2) was observed at -173 °C.

1,2-Dihalodigermenes bearing bulky Eind groups: synthesis, characterization, and conversion to halogermylenoids.

1,2-Dihalodigermenes, (E)-(Eind)XGe[double bond, length as m-dash]GeX(Eind) (X = Br and Cl), bearing the fused-ring bulky Eind group (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) have been isolated as orange-yellow crystals by the ligand redistribution reaction between the diarylgermylene, (Eind)2Ge:, and GeX2·dioxane in toluene via the cleavage and recombination of the Ge-C and Ge-X bonds. The dihalodigermenes have a Ge[double bond, length as m-dash]Ge double bond character in the crystalline state, but dissociate into halogermylenes, (Eind)XGe:, in solution. The addition of excess LiBr to the THF solution of the bromogermylene, (Eind)BrGe:, led to the formation of an equilibrium mixture containing the lithium bromogermylenoid, [Li+][(Eind)GeBr2]-. The bromogermylenoid can be isolated as a cryptand-separated potassium ion pair, [K+(crypt-222)][(Eind)GeBr2]-, which has been structurally characterized.

Luminescent Tb(iii) and Sm(iii) complexes with a 1,4,7-triazacyclononane-based tris-aryloxide ligand for high-performance oxygen sensors.

Taking advantage of the outstanding oxygen-sensitive luminescence properties of the previously synthesised Tb(iii) complex [{(MeMeArO)3tacn}LnIII(THF)] (1Tb, Ln = Tb), herein, we have prepared an oxygen sensor based on 1Tb embedded in polystyrene film (1Tb/PS) and found that 1Tb/PS shows the highest sensitivity (I0/I100 = 14.9) and the fastest response (response/recovery time = 1.9 s/2.9 s), among the lanthanide(iii)-based oxygen sensors with f-f emission. Moreover, we have prepared the lanthanide(iii)-based colorimetric luminescent oxygen sensor (1TbSm/PS) with green-yellow-red responses, by using 1Tb and a newly synthesised oxygen-insensitive Sm(iii) complex (1Sm, Ln = Sm; Φ = 0.010 and τ = 12.2 µs).

Control of Lanthanide Coordination Environment: Synthesis, Structure, and Oxygen-Sensitive Luminescence Properties of an Eight-Coordinate Tb(III) Complex.

Coordination environment of the Tb(3+) ion in oxygen-sensitive luminescent complexes can be successfully controlled through the size of alkyl substituents on ligands {((RMe)ArOH)4cyclen} (R = tBu or Me; cyclen = 1,4,7,10-tetraazacyclododecane); a newly prepared eight-coordinate complex 1(tBu) shows higher oxygen sensitivity (KSV = 17 600) and lower luminescence quantum yield (Φ = 0.67 under N2) than those of the previously reported seven-coordinate analogues 1(Me) and [{((MeMe)ArO)3tacn}Tb(III)(THF)] (KSV = 12 600 and 8300, Φ = 0.91 and 0.91 under N2, respectively; tacn = 1,4,7-triazacyclononane; THF = tetrahydrofuran). The oxygen-sensitive mechanism is discussed on the basis of the photophysical properties of the corresponding Gd(III) complexes.

Inorganic clusters with a [Fe2MoOS3] core-a functional model for acetylene reduction by nitrogenases.

We report the first example of a wholly inorganic mimic of a part of the FeMoco active centre of nitrogenases. We detail the synthesis, characterisation and reactivity of two related, transient hydride-containing inorganic clusters, a dihydride complex and a vinyl monohydride complex, which bear the [Fe2MoOS3] portion of FeMoco. The dihydride complex is capable of reducing acetylene to ethylene via the vinyl monohydride complex. In the reaction cycle, a transient low-valent complex was generated by the reductive elimination of H2 or ethylene from dihydride or vinyl monohydride complexes, respectively.

An oxygen-sensitive luminescent Dy(iii) complex.

This paper presents the first dysprosium(iii) complex, [{((MeMe)ArO)3tacn}Dy(III)(THF)] (1(Dy)), that shows oxygen-sensitive luminescence. The synthesis, structure and oxygen-sensitive luminescence properties of 1(Dy) are reported (Φ = 0.050 and τ = 17.7 µs under N2, Φ = 0.011 and τ = 4.1 µs under O2 and KSV = 305 M(-1) in THF; KSV = 0.0077%(-1) in polystyrene film). The oxygen sensitive mechanism of 1(Dy) is discussed based on the photophysical properties of the corresponding gadolinium(iii) complex, [{((MeMe)ArO)3tacn}Gd(III)(THF)].

A gadolinium(iii) complex that shows room-temperature phosphorescence in the crystalline state.

This paper presents a gadolinium(iii) complex that shows blue phosphorescence in the crystalline state at room temperature under air atmosphere; color of the crystals can be changed to pale-green from blue by doping of 1-naphthol.

Photoinduced bending of rod-like millimetre-size crystals of a rhodium dithionite complex with n-pentyl moieties.

Rod-like millimetre-size crystals of a newly prepared rhodium dithionite complex with n-pentyl moieties bend upon photoirradiation and return to the initial shape upon heating; the roles of the flexible n-pentyl moieties as well as the photoreactive dithionite unit (µ-O2SSO2) are disclosed by single crystal X-ray diffraction.

A High-Valent Iron(IV) Peroxo Core Derived from O2.

Dioxygen-tolerant [NiFe] hydrogenases catalyze not only the conversion of H2 into 2 H(+) and 2 e(-) but also the reduction of O2 to H2O. Chemists have sought to mimic such bifunctional catalysts with structurally simpler compounds to facilitate analysis and improvement. Herein, we report a new [NiFe]-based catalyst for O2 reduction via an O2 adduct. Structural investigations reveal the first example of a side-on iron(IV) peroxo complex.

An IrSi oxide film as a highly active water-oxidation catalyst in acidic media.

We report an acid-stable Si oxide-doped Ir oxide film (IrSi oxide film), made by metal organic chemical vapour deposition (MOCVD) of an Ir(V) complex for electrochemical water-oxidation. This is a successful improvement of catalytic ability and stability depending upon the pH of Ir oxide by doping of Si oxide. The turnover frequency (TOF) of the electrochemical water-oxidation by the IrSi oxide film is the highest of any Si oxide-doped Ir oxide materials and higher even than that of Ir oxide in acidic media.

A macrocyclic tetraamine bearing four phenol groups: a new class of heptadentate ligands to provide an oxygen-sensitive luminescent Tb(III) complex with an extendable phenol pendant arm.

This paper presents a 1,4,7,10-teraazacyclododecane-based tetrakis-phenol as a protonated ligand precursor and its oxygen-sensitive luminescent terbium(III) complex with an extendable phenol pendant arm (Φ = 0.91 under N2, Φ = 0.031 under air), in which the potentially N4O4-octadentate ligand unprecedentedly coordinates to the Tb(3+) ion in a N4O3-heptadentate fashion.