Linear trimetal complexes of the ligand 2,2'-dipyridylamide /
The ligand 2,2'-dipyridylamide (dpa) stabilizes linear trinuclear chains of Cr, Co, Ni, Cu, Ru, and Rh atoms in complexes of the type M₃(dpa)₄Cl₂. The electronic structures of these complexes are described in terms of either electron localization on each metal atom or delocalization across the...
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
2004.
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| Subjects: | |
| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=766020651&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | The ligand 2,2'-dipyridylamide (dpa) stabilizes linear trinuclear chains of Cr, Co, Ni, Cu, Ru, and Rh atoms in complexes of the type M₃(dpa)₄Cl₂. The electronic structures of these complexes are described in terms of either electron localization on each metal atom or delocalization across the trimetal chain. Oxidation of Ni₃(dpa)₄Cl₂ to [Ni₃(dpa)₄](PF₆)₃ occurs with a change from a localized electronic structure in the former to a delocalized system with 3-center Ni-Ni bonding in the latter. Oxidation of the analogous tricopper compound to [Cu₃(dpa)₄Cl₂]SbCl₆ does not involve this sort of change, and the CuĊ̇̇u separations become longer due to increased electrostatic repulsion in the Cu₃⁷⁺ core. It is possible to exchange the axial chloride ions in M₃(dpa)₄Cl₂ complexes for other pseudohalogens, neutral acetonitrile molecules, and acetylide ions. The bis-phenylacetylide complexes, M₃(dpa)₄(CCPh)₂, have remarkably low oxidation potentials compared to the chloro analogues, and serve as prototypes for other acetylide complexes. In one such complex, Co₃(dpa)₄(FAC)₂ (FAC = ferrocenylacetylide) metal atoms appended to the trimetal chain allow us to examine the extent of communication from one end of the chain to the other, though the results of this test are not straightforward. |
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| Item Description: | Vita. "Major Subject: Chemistry". |
| Physical Description: | xvii, 189 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilm Inc. |
| Bibliography: | Includes bibliographical references (leaves 174-181). |