Ruthenium and osmium carbonyl nitrosyl complexes: Matrix infrared spectra and density functional calculations for M(CO)2(NO)2 and M(CO)(NO) (M=Ru, Os)

Isocyanate Formation from Reactions of Early Lanthanide Metal Atoms with NO and CO in Solid Argon

“…The reactions of metal atoms with NO and CO serve as the simplest model in understanding the intrinsic mechanism of catalytic NO and CO reduction processes. Previous matrix isolation infrared spectroscopic studies on the reactions of transition-metal atoms with CO and NO mixtures show that some metal atoms react with NO and CO to form unsaturated metal carbonyl nitrosyl complexes. − The end-on bonded M­(CO)­(NO) complexes isomerize to the side-on bonded M­(CO)­(η 2 -NO) complexes, which serve as precursors for the insertion reaction that leads to the reduction of NO and the formation of isocyanate OMNCO species. − Here we report a combined matrix isolation infrared spectroscopic and theoretical study on the reactions of early lanthanide metal atoms with NO and CO mixtures in solid argon. We will show that the reactions proceed with the initial formation of inserted NLnO species, which subsequently react with CO to form the NLnO­(CO) complexes.…”

Octacoordinate metal carbonyls of scandium and yttrium: theoretical calculations and experimental observation

“…The typical experimental methods involved generating transition metal carbonyls through reactions of a single metal ion or atom with CO, and then characterizing the products using mass spectrometry, infrared dissociation spectroscopy and photoelectron spectroscopy in the gas phase, [5][6][7][8][9][10][11][12][13] or infrared absorption spectroscopy in matrix. [3,[14][15][16][17][18] At the same time, Density Functional Theory (DFT) calculations combined with the experiments have been effective in predicting the structures and bonding of these complexes.Except a very few special species, [5] most saturated transition metal carbonyls satisfy the 18-electron rule, in which the electrons from the central metal atom and the ligands form the d 10 s 2 p 6 noble gas configuration. Typical examples include neutral Ni(CO) 4 , Fe(CO) 5 and Cr(CO) 6 , and the cationic Cu(CO) 4 + , Co(CO) 5 + and Mn(CO) 6 + .…”

“…With the development of techniques for gas‐phase experiments and matrix‐isolation, more saturated and unsaturated metal carbonyls have been generated and characterized. The typical experimental methods involved generating transition metal carbonyls through reactions of a single metal ion or atom with CO, and then characterizing the products using mass spectrometry, infrared dissociation spectroscopy and photoelectron spectroscopy in the gas phase, or infrared absorption spectroscopy in matrix . At the same time, Density Functional Theory (DFT) calculations combined with the experiments have been effective in predicting the structures and bonding of these complexes.…”

Metal Oxo-Fluoride Molecules OnMF2 (M = Mn and Fe; n = 1–4) and O2MnF: Matrix Infrared Spectra and Quantum Chemistry

“…16 O 3 was prepared from 16 O 2 (99.999%, British Oxygen Company) by tesla coil discharge (about 1 Torr) in a 2 L Pyrex bulb, condensed by liquid nitrogen, and evacuated before dilution with research-grade neon and argon. A sample of 18 O 3 and a mixture of 16,18 O 3 were similarly generated using 18 O 2 (>99%, Shanghai Research Institute of Chemical Industry) and a mixture of 16 O 2 and 18 O 2 (1:1), respectively. The mixture of 16,18 O 3 was converted into a mixture of 16 O 2 , 16 O 18 O, and 18 O 2 (1:2:1) by full-arc photolysis for ≥30 min.…”