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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)
DOI:https://doi.org/10.1021/ja00246a009· OSTI ID:6386004
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