Multiphoton Ionization of Group VI B hexacarbonyl Van Der Waals Clusters: Trends in Intracluster Photochemistry
Abstract
Van der Waals clusters of M(CO)6 (M = Cr, Mo, W) generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization (MPI) and the product ions analyzed by quadrupole mass spectrometry. We previously observed efficient production of MoO+ and MoO2+ following MPI of Mo (CO) 6 van der Waals clusters. We proposed that these ions arise through novel reactions between a neutral photoproduced metal atom and the ligands of an adjacent metal carbonyl solvent molecule within the cluster. In order to test some of the predictions of this model, we have examined the MPI of van der Waals clusters of the other Group VIB hexacarbonyls. We find the same novel behavior (viz., efficient production of metal oxide ions) in the W(CO)6 system as that previously observed for Mo(CO)6. However, we find no evidence of such behavior in the Cr(CO)6 system. These observations suggest that the reactivity of first-row transition metal atoms may be fundamentally different from that of second- or third-row metals. Metal carbonyls, Chromium, Tungsten, Molybdenum.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 13, 1989
- Accession Number
- ADA208669
Entities
People
- James F. Garvey
- William R. Peifer
Organizations
- University at Buffalo