Substitution of CO with PF$\sb3$ in the Group VIIB dimetal decacarbonyls has been studied under thermal and photolytic conditions. Substitution via photolysis is faster and results in the production of a greater number of isomers. Under both thermal and photolytic conditions, a maximum of four CO ligands may be replaced with PF$\sb3$ in Mn$\sb2$(CO)$\sb{10}$. At least eight of the carbon monoxides can be replaced in Tc$\sb2$(CO)$\sb{10}$, whereas Re$\sb2$(CO)$\sb{10}$ can be fully substituted with PF$\sb3$. Under thermal conditions the rate of reaction proceeds Tc $\gg$ Re $>$ Mn at 130$\sp\circ$C, while under photolytic conditions Tc $\gg$ Mn $>$ Re. For Mn, the metal-metal bond strength does not vary within experimental error from the parent upon the substitution of a single CO with PF$\sb3$. The mixed-metal decacarbonyls, MnTc(CO)$\sb{10}$, MnRe(CO)$\sb{10}$, and ReTc(CO)$\sb{10}$ were synthesized and their reaction with PF$\sb3$ investigated. The possible mechanisms for substitution are reexamined, based upon the observed products. / Source: Dissertation Abstracts International, Volume: 49-07, Section: B, page: 2638. / Major Professor: Ronald J. Clark. / Thesis (Ph.D.)--The Florida State University, 1988.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77811 |
| Contributors | Grimm, Casey Craig., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 166 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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