Terminal Iron Carbyne Complexes Derived from Arrested CO₂ Reductive Disproportionation

Abstract

The encumbered tetraisocyanide dianion Na [Fe(CNArMes2 ) ] reacts with two molecules of CO to effect reductive disproportionation to CO and carbonate ([CO ] ). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono-CO adduct. This results in the formation of four-coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment of an C(O)OSiR group to an isocyanide nitrogen atom. Crystallographic, spectroscopic, and computational analyses of these iron-carbon multiply bonded species reveal electronic structure properties indicative of a conformationally locked iron carbyne unit.

Oxidorhenium(V) and Rhenium(III) Complexes with m‐Terphenyl Isocyanides

“…But the example of the Re(III) complex also shows that the corresponding IR frequencies are sensitive to other structural features such as the trans ligand (here Cl – vs. PPh 3 ). Similar findings have been reported earlier for various complexes with m ‐terphenylisocyanides . Thus, the absolute values of these stretches should be regarded with suspicion in the discussion of the bonding situation in such compounds.…”

“…m ‐Terphenyl isocyanides have been shown to be useful ancillary ligands for the isolation of unusual and highly reactive transition metal complexes . These encumbering ligands stabilize transition metal centers featuring high degrees of coordinative and electronic unsaturation.…”

Preparation, Structure, Photoluminescent and Semiconductive Properties, and Theoretical Calculation of a Novel Cadmium Complex with Mixed Ligands

“…Powder-like barium sulfate acts as a reference for 100% reflectance and finely-ground powder sample was coated on the surface of the barium sulfate. After measuring the solid-state UV/vis diffuse reflectance spectra, the data was treated carefully with the Kubelka-Munk function which is known as α/S = (1 -R) 2 /2R. With regard to this function, α means the absorption coefficient, S refers to the scattering coefficient which is actually wavelength independent when the size of the particle is larger than 5 µm, and the R is related to the reflectance.…”

Preparation, Structure, Photoluminescent and Semiconductive Properties, and Theoretical Calculation of a Mononuclear Nickel Complex with 3-Hydroxy-2- Methylquinoline-4-Carboxylato Ligand

“…In recent years, metallo-organic coordination polymers have attracted considerable interest due to their diverse structures and potential applications in fluorescence, magnetic materials, gas adsorption, catalysis and medicine and so forth. [1][2][3][4][5][6] The synthesis of coordination polymers with specific functions has gradually become a research hotspot in the field of material chemistry. 7 From the perspective of crystal engineering, the most useful and facile way to construct coordination complexes is to adopt a suitable ligand to connect metal centers.…”