Characterization of a Reactive Rh2 Nitrenoid by Crystalline Matrix Isolation

Here we report the first X-ray crystal structure of a reactive Rh₂ nitrenoid, enabled by N₂ elimination from an organic azide ligand within a single-crystal matrix. The resulting high-resolution data set demonstrates a long Rh–N bond, consistent with a triplet electronic structure. The demonstration of facile access to reactive metal nitrenoids within a crystalline matrix provides a platform for structural characterization of the elusive transient species at the heart of C–H functionalization.

Characterization of a Reactive Rh2 Nitrenoid by Crystalline Matrix Isolation

Here we report the first X-ray crystal structure of a reactive Rh₂ nitrenoid, enabled by N₂ elimination from an organic azide ligand within a single-crystal matrix. The resulting high-resolution data set demonstrates a long Rh–N bond, consistent with a triplet electronic structure. The demonstration of facile access to reactive metal nitrenoids within a crystalline matrix provides a platform for structural characterization of the elusive transient species at the heart of C–H functionalization.

Cyanide and Azide Anion Complexation by a Bidentate Stibonium-Borane Lewis Acid

Our ongoing interest in the chemistry of polyfunctional Lewis acids has led us to investigate the reaction of the stibonium-borane [o-(Ph2MeSb)(Mes2B)C6H4]+ (1+) with cyanide and azide, two toxic anions. Both anions react with 1+ to afford the corresponding neutral complexes 1-CN and 1-N3. Structural and computational studies show that the coordinated anion interacts with both the boron and antimony atoms of the bidentate Lewis acid. While the azide complex features a typical κ2N1 : N1 bridging azide ligand, the cyanide complex possesses a cyanoborate moiety whose cyanide interacts side-on with the stibonium center. The Lewis acid-anion interactions observed in these complexes have also been studied computationally using the Natural Bond Orbital method

Topological analysis of the three-dimensional coordination polymer poly[(μ4-azido)[μ4-5-(pyridin-4-yl)tetrazolido]disilver(I)]

The title compound, [Ag2(C6H4N4)(N3)]n, was obtained under hydrothermal conditions at 433 K. The asymmetric unit of the orthorhombic space group (Pna21) consists of two Ag+cations, an anionic 5-(pyridin-4-yl)tetrazolide (4-ptz−) ligand and an anionic azide ligand. Both Ag+centres are coordinated by four N atoms, forming a distorted tetrahedral coordination environment. When all the component ions are viewed as 4-connected nodes, the whole three-dimensional network can be regarded topologically as a new kind of 4,4,4,4-connected net with the Schläfli symbol (4.85)(42.84)(43.83)2.

{μ-2-[(3-Amino-2,2-dimethylpropyl)iminomethyl]-6-methoxyphenolato-1:2κ5O1,O6:N,N′,O1}{2-[(3-amino-2,2-dimethylpropyl)iminomethyl]-6-methoxyphenolato-1κ3N,N′,O1}-μ-azido-1:2κ2N:N-azido-2κN-methanol-2κO-dinickel(II)

Two distinct coordination geometries are found in the binuclear title complex, [Ni2(C13H19N2O2)2(N3)2(CH3OH)], as one Schiff base ligand is pentadentate, coordinatingviathe anticipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the methoxy O atom. The NiIIatoms are linked by a μ2-oxide atom and one end of a μ2-azide ligand, forming an Ni2ON core. The coordination geometry for the NiIIatom coordinated by the tridentate ligand is completed by the methoxy O atom derived from the pentadentate ligand, with the resulting N3O3donor set defining afacoctahedron. The second NiIIatom has itscis-octahedral N4O2coordination geometry completed by the imine N and amine N atoms of the pentadentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intramolecular hydrogen bond between the methanol H and the oxide O atom. Linear supramolecular chains along theaaxis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

The Electronic Structures and Magnetic Properties of Co(endi)2(N3)2

The electronic structures and magnetic properties of the compound Co(endi)2(N3)2 are studied by means of the first-principles method. According to the calculations, there is ferromagnetic interaction in the compound, and the magnetic coupling comes from the spin delocalization effect from Co2+ to the azide ligand. It is found that there is strong intralayer and weak interlayer magnetic couplings in the compound. It also reveals semi-metallically magnetic properties.