Electron paramagnetic resonance spectrum of Cu(CO)/sub 3/: an inorganic isolobal analogue of methyl

Journal Article · Thu Mar 13 04:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100278a014· OSTI ID:5816459

Howard, J A; Mile, B; Morton, J R; Preston, K F; Sutcliffe, R

Copper tricarbonyl, Cu(CO)/sub 3/, has been prepared on a rotating cryostat by reacting /sup 63/Cu atoms with CO on either a cyclohexane or adamantane surface at 77 K. Its EPR spectrum (4-77 K) yielded the following parameters: g/sub xx/ = g/sub yy/ = 2.0028, g/sub zz/ = 2.0010; for /sup 63/Cu, a/sub xx/ = a/sub yy/ approx. = 0 MHz, a/sub zz/ = 225 MHz; for /sup 13/C, a/sub xx/ = a/sub yy/ = 29 MHz, a/sub zz/ = 8 MHz. The spectrum of Cu(CO)/sub 3/ in adamantane was isotropic at 223 K, yielding the following parameters: g/sub iso/ = 2.0014, a/sub 63/ = 93.9 MHz, a/sub 13/(3) = 22.0 MHz. Cu(CO)/sub 3/ is a planar molecule belonging to the A/sub 2/ representation in D/sub 3h/ symmetry. Most of the unpaired electron is in the Cu 4p/sub z/ orbital perpendicular to the molecular plane. There is a marked temperature dependence of the isotropic copper hyperfine interaction, which increases from 75 MHz at 4 K to 98 MHz at 250 K. This is attributed to an out-of-plane vibration of the radical which modulates the isotropic copper hyperfine interaction. An analysis of this effect yields a nu/sub 2/ vibration frequency of approx. 300 cm/sup -1/. Cu(CO)/sub 3/ is stable to decomposition or dimerization in adamantane up to at least 263 K and may provide a suitable vehicle for incorporating copper into inert supports for catalytic purposes. 23 references, 5 figures, 2 tables.

• Research Organization: National Research Council of Canada, Ottawa, Ontario
• OSTI ID: 5816459
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:6; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ADAMANTANE
ALKANES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL PREPARATION
CONTROL EQUIPMENT
COPPER 63
COPPER COMPOUNDS
COPPER ISOTOPES
CRYOSTATS
CYCLOALKANES
CYCLOHEXANE
DATA
DEUTERIUM COMPOUNDS
ELECTRON SPIN RESONANCE
ENERGY LEVELS
EQUIPMENT
EXCITED STATES
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN COMPOUNDS
HYPERFINE STRUCTURE
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPE ENRICHED MATERIALS
ISOTOPES
LOW TEMPERATURE
MAGNETIC RESONANCE
MATERIALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SORPTIVE PROPERTIES
STABLE ISOTOPES
SURFACE PROPERTIES
SYNTHESIS
TEMPERATURE DEPENDENCE
THERMOSTATS
TRANSITION ELEMENT COMPOUNDS
VIBRATIONAL STATES