Determination of carbide, carbyne, and carbene bond energies by gas-phase photodissociation of RhCH/sub 2//sup +/, NbCH/sub 2//sup +/, and LaCH/sub 2//sup +/
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Three photoproducts, MCH/sup +/, MC/sup +/, and M/sup +/ are observed in the photodissociation of MCH/sub 2//sup +/ (M = Rh, Nb, and La). In contrast, the low-energy collision-induced dissociation of RhCH/sub 2//sup +/ and NbCH/sub 2//sup +/ yields MC/sup +/ and M/sup +/ whereas LaCH/sub 2//sup +/ produces only La/sup +/. Each photodissociation spectrum reveals two peaks: 240 nm (sigma = 0.06 A/sup 2/) and 280 nm for RhCH/sub 2//sup +/, 240 nm (sigma = 0.20 A/sup 2/) and 390 nm for NbCH/sub 2//sup +/, and 260 nm (sigma = 0.19 A/sup 2/) and 320 nm for LaCH/sub 2//sup +/. Photoappearance thresholds for the products yield bond energies for M/sup +/-CH/sub 2/, M/sup +/-CH, and m/sup +/-C for each metal ion. Ionization potentials for RhC, NbC, and LaC are calculated on the basis of D/sup 0/(M-C) and D/sup 0/(M/sup +/-C). Plots of metal-ion ligand bond energies vs. bond energies for corresponding carbon analogs show linear correlation and allow bond order predictions to be made for the metal complexes.
- Research Organization:
- Purdue Univ., West Lafayette, IN
- DOE Contract Number:
- AC02-80ER10689
- OSTI ID:
- 6386004
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:12; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
BINDING ENERGY
CARBENES
CARBIDES
CARBON COMPOUNDS
CARBYNES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISSOCIATION
ENERGY
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
IONIZATION POTENTIAL
IONS
LANTHANUM COMPLEXES
LIGANDS
NIOBIUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADICALS
RARE EARTH COMPLEXES
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
400500* -- Photochemistry
BINDING ENERGY
CARBENES
CARBIDES
CARBON COMPOUNDS
CARBYNES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISSOCIATION
ENERGY
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
IONIZATION POTENTIAL
IONS
LANTHANUM COMPLEXES
LIGANDS
NIOBIUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADICALS
RARE EARTH COMPLEXES
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES