Insertion reactions of carbon dioxide with square planar transition metal complexes /
| Main Author: | |
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| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1988.
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| Subjects: | |
| Online Access: | ProQuest, Abstract Link to OAKTrust copy |
| Abstract: | The reactivity of several complexes of the type L2MR2 (M Pd, Mi) and L3M'R (M' - Rh, Ir) (L - phosphine; R- hydride, alkyl, aryl) towards CO2 was studied using such techniques as high-pressure, in-situ IR and high-pressure NMR. WE established a general order of reactivity of bonds towards CO2 insertion to form metallocarboxylates: metal-hydride > metal-methyl > metal-phenyl. Complexes containing highly electron-withdrawing ligands such as phenoxides, halides, or carboxylates trans to the hydride, did not insert CO2. Overall, carbonxylation reactions were found to be highly dependent upon both, the electronic and the steric environment of the meal center. Hence, the reactivity for the supporting ligands L decreases in the order PMe3 > Pet3 > PPh3 > CO. Comparative studies involving rhodium nd iridium complexes showed decreasing reactivity down the triad due to strengthening of metal- carbon bonds. Based upon the above findings, we postulated an associative interchange (I[A]) mechanism involving initial interaction of CO2 with the metal center... |
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| Item Description: | Typescript (photocopy). Vita. "Major subject: Chemistry." |
| Physical Description: | xv, 139 leaves : illustrations ; 29 cm |
| Bibliography: | Includes bibliographical references. |