A spectroscopic study of the reaction of Cu atoms with CO in a rotating cryostat: Evidence for the formation of CuCO, Cu(CO) sub 3 , and Cu sub 2 (CO) sub 6

Journal Article · Thu Jan 12 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100338a026· OSTI ID:5296687

Chenier, J H.B.; Hampson, C A; Howard, J A; Mile, B ^[1]

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1. National Research Council, Ottawa, Ontario (Canada)

Reaction of {sup 63}Cu atoms with CO has been studied in inert hydrocarbon matrices in a rotating cryostat at 77 K at EPR, FTIR, and UV/visible spectroscopy. CuCO and Cu(CO){sub 3} have been identified by EPR spectroscopy. CuCO has the magnetic parameters a{sub 63} = 3961 MHz, a{sub 13} = 191 MHz, and g = 1.9966 and is a linear molecule with most of the unpaired spin located in an sp-hybridized orbital on Cu. It is unstable and disappears rapidly above 77 K. Cu(CO){sub 3} is a planar trigonal {pi} radical with a {sup 2}A{sub 2}{prime}{prime} electronic ground state and a{sub 17} = 11.2 MHz which indicates significant unpaired spin population on the ligands. It has three infrared bands at 1998, 1988, and 1978 cm{sup {minus}1} which are assigned to the CO stretching mode of a D{sub 3h} molecule in three different trapping sites and is significantly more stable than CuCO. There are no bands in the FTIR spectra from Cu(CO){sub 2}. Cu{sub 2}(CO){sub 6} is formed in significant yields in adamantane and cyclohexane at 77 K and has a major CO stretching mode at 2035 cm{sup {minus}1}. Optical spectra of Cu(CO){sub 3} and Cu{sub 2}(CO){sub 6} in adamantane have {sup 2}A{sub 1}{prime} {l arrow} {sup 2}A{sub 2}{prime}{prime} and {sigma}* {l arrow} {sigma} electronic transitions at 565 and 405 nm, respectively.

• OSTI ID: 5296687
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:1; ISSN JPCHA; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COPPER
COPPER 63
COPPER ISOTOPES
DATA
ELECTRON SPIN RESONANCE
ELEMENTS
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
INFORMATION
INFRARED SPECTRA
INTERMEDIATE MASS NUCLEI
ISOTOPES
LOW TEMPERATURE
MAGNETIC PROPERTIES
MAGNETIC RESONANCE
MEASURING INSTRUMENTS
METALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
RESONANCE
SPECTRA
SPECTROMETERS
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENTS
ULTRALOW TEMPERATURE