Silylamido supported dinitrogen heterobimetallic complexes: Syntheses and their catalytic ability

Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(Me3Si)N]3MoN2Mg(THF)2[N(SiMe3)Ar] (5) and [Ar(Me3Si)N]3MoN2SiMe3 (6) (Ar = 3,5-Me2C6H3) were synthesized and structurally characterized, which were proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. 1H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating the possible catalytic ability of Mo-N = N motif.

A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction

<p>The detection of perchlorate (ClO₄⁻) on and beyond Earth requires ClO₄⁻ reduction technologies to support water purification and space exploration. However, the reduction of ClO₄⁻ usually entails either harsh conditions or multi-component enzymatic processes. We developed a heterogeneous Mo−Pd/C catalyst from sodium molybdate to reduce aqueous ClO₄⁻ into Cl⁻ with 1 atm H₂ at room temperature. Upon hydrogenation by H₂/Pd, the reduced Mo oxide species and a bidentate nitrogen ligand (1:1 molar ratio) are transformed <i>in situ</i> into oligomeric Mo sites on the carbon support. The turnover number and frequency for oxygen atom transfer from ClO_x⁻ substrates reached 3850 and 165 h⁻¹ on each Mo site. This simple bioinspired design yielded a robust water-compatible catalyst for the removal and utilization of ClO₄⁻.</p>

A Bioinspired Molybdenum Catalyst for Aqueous Perchlorate Reduction

<p>The detection of perchlorate (ClO₄⁻) on and beyond Earth requires ClO₄⁻ reduction technologies to support water purification and space exploration. However, the reduction of ClO₄⁻ usually entails either harsh conditions or multi-component enzymatic processes. We developed a heterogeneous Mo−Pd/C catalyst from sodium molybdate to reduce aqueous ClO₄⁻ into Cl⁻ with 1 atm H₂ at room temperature. Upon hydrogenation by H₂/Pd, the reduced Mo oxide species and a bidentate nitrogen ligand (1:1 molar ratio) are transformed <i>in situ</i> into oligomeric Mo sites on the carbon support. The turnover number and frequency for oxygen atom transfer from ClO_x⁻ substrates reached 3850 and 165 h⁻¹ on each Mo site. This simple bioinspired design yielded a robust water-compatible catalyst for the removal and utilization of ClO₄⁻.</p>

A Platinum(II) Metallonitrene with a Triplet Ground State

<div><div><div><p>Metallonitrenes (M–N) are complexes with a subvalent, atomic nitrogen ligand that have been proposed as key reactive intermediates in nitrogen atom transfer reactions. However, in contrast to the common class of nitride complexes (Mo≡N) and organic nitrenes (R–N), authentic, persistent metallonitrenes remain elusive. We here report that the photolysis of a platinum(II) pincer azide complex enabled the crystallographic, spectroscopic, magnetic and computational characterization of a metallonitrene that is best described as a singly bonded, atomic nitrogen diradical ligand bound to platinum(II). The photoproduct exhibits selective C–H, B–H, and B–C nitrogen atom insertion reactivity. Mechanistic examination of aldehyde C–H amidation surprisingly reveals nucleophilic reactivity of the subvalent N-diradical ligand.<br></p></div></div></div>

A Platinum(II) Metallonitrene with a Triplet Ground State

<div><div><div><p>Metallonitrenes (M–N) are complexes with a subvalent, atomic nitrogen ligand that have been proposed as key reactive intermediates in nitrogen atom transfer reactions. However, in contrast to the common class of nitride complexes (Mo≡N) and organic nitrenes (R–N), authentic, persistent metallonitrenes remain elusive. We here report that the photolysis of a platinum(II) pincer azide complex enabled the crystallographic, spectroscopic, magnetic and computational characterization of a metallonitrene that is best described as a singly bonded, atomic nitrogen diradical ligand bound to platinum(II). The photoproduct exhibits selective C–H, B–H, and B–C nitrogen atom insertion reactivity. Mechanistic examination of aldehyde C–H amidation surprisingly reveals nucleophilic reactivity of the subvalent N-diradical ligand.<br></p></div></div></div>

A versatile nitrogen ligand for alkaline-earth chemistry

A readily available and versatile bis(imino)carbazolate ligand is shown to allow for the synthesis of a broad range of solution stable heteroleptic complexes of the alkaline-earth metals Mg, Ca, Sr and Ba.

Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane

Two dinitrosyl iron and cobalt complexes [Fe(NO)2(L1”)](BF4) and [Co(NO)2(L1”)](BF4) are synthesized and characterized, supported by a less hindered bidentate nitrogen ligand bis(3,5-diisopropyl-1-pyrazolyl)methane (denoted as L1”), are surprisingly stable under argon atmosphere. X-ray structural analysis shows a distorted tetrahedral geometry. Spectroscopic and structural parameters of the dinitrosyl iron and cobalt complexes are consistent with the previous reported {Fe(NO)2}9 and {Co(NO)2}10. Two N–O and M–N(O) stretching frequencies and their magnetic properties are also consistent with the above electronic structural assignments. We explored the dioxygen reactivities of the obtained dinitrosyl complexes. Moreover, the related [FeCl2(L1”)], [Co(NO3)2(L1”)], and [Co(NO2)2(L1”)] complexes are also characterized in detail.