Organometallic chemistry of low-valent d8 and d10 complexes in aqueous solution /
Studies have been carried out on the water soluble ligand,
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
1997.
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| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=739887401&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | Studies have been carried out on the water soluble ligand, 1,3,5-triaza-7-phosphaadamantane, PTA, and a series of d10 metal-PTA complexes to determine the effect of PTA binding to the metal center via the phosphorus atom on the basicity of the nitrogen atoms of the ligand. Potentiometric titrations of PTA, O=PTA, and the complexes Pd11Cl2(PTA)2, [Pd11Cl(PTA)3]Cl, Pd0(PTA)4, and Pt0(PTA)4 with a standardized solution of HCl(O.lM) were performed to determine the respective pKa's of the compounds. It was demonstrated that PTA when phosphorus bound to [M+2] centers is less basic, i.e., has a lower pka, than when correspondingly bound in [M0] speices. Furthermore, trends in basicity of the nitrogen atoms in PTA were established, where the basicity decreases in the following order: PTA-Pt complexes > their Pd analogs, and PTA > its oxide, O=PTA. A series of water-soluble transition-metal complexes, utilizing PTA and meta-sulfonatophenyidiphenylphosphine (TPPMS), were synthesized and their properties and reactivities were investigated. The complexes cis- PdCl2(PTA)2, [PdCl(PTA)3]Cl, [Pd(PTAH)4]Cl4, [Pt(PTAH)4]Cl4, and [Ni(NO)(PTA)3]BPh4, have all been structurally characterized by single-crystal x-ray diffraction studies. NMR, infrared, and UV-visible spectoscopic techniques were employed to study the reactivities of the transition metal complexes in aqueous solution. Water-soluble analogs of Vaska's complex, trans-lr(CO)Cl(PPh3)2, were synthesized, and their reactivities were investigated in aqueous solution. The complex trans-lr(CO)Cl(TPPMS)2 has been structurally characterized by single-crystal x-ray diffraction studies. NMR, infrared, UV-visible spectrophotometric techniques, and pH titrametric measurements were employed to study the properties and reactivities of these complexes in aqueous solutions. Although generally similar in reacitvity with acids and ethylene, the reactions of lr(CO)Cl(TPPMS)2 with dihydrogen and dioxygen are irreversible in water. This can be attributed to the interaction of water with both the metal complex and the substrate. |
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| Item Description: | Vita. "Major Subject: Chemistry". In title, numerals are used. |
| Physical Description: | xii, 129 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilms Inc. |
| Bibliography: | Includes bibliographical references: pages 95-100. |