The chemistry of trifluorophosphine containing complexes is interesting because of the similar bonding properties of PF(,3) and CO. Both are capable of pi back-bonding with transition metals. A series of PF(,3) substituted compounds, M(PF(,3))(,x)(CO)(,6-x), where M = Cr, Mo and W and x = 0 to 4, were synthesized and separated in our laboratory. The analytical separation of these compounds was investigated and quantified by gas chromatography. Separation of each different compound, X, was achieved as well as separation of the geometrical isomers at x = 2 and 3. A series of investigations into the reaction chemistry of these compounds was conducted at different energy inputs. The thermally induced isomerization reactions of cis and trans-M(PF(,3))(,2)(CO)(,4) was quantitatively followed and all pertinent kinetic parameters calculated. The rates of reaction were found to be dependent on the steric interactions of the phosphine ligands and metal size. Equilibrium concentrations of the cis and trans isomers are proposed to be dependent on steric interactions as well as electronic considerations. The reaction chemistry of tungsten trifluorophosphine carbonyls following neutron capture was studied. Irradiations of these compounds in the condensed and gas phase were conducted, with and without excess ligand gas. Methods were developed to be able to detect the trace amounts of scrambled products. A mechanism is proposed to account for the differing chemistries of PF(,3) and CO in this energy regime. / Source: Dissertation Abstracts International, Volume: 45-11, Section: B, page: 3486. / Thesis (Ph.D.)--The Florida State University, 1985.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_75455 |
| Contributors | DENHAM, ELIZABETH LEIGH., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 239 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
Page generated in 0.0011 seconds