Low nuclearity complexes of gold, copper, and iron with organophosphor-1,1-dithiolato type ligands : synthesis, structure, reactivity, and luminescence properties /
characterization of new dithiophosphonate salts and their capacity to facilitate metal complex formation both in the organic and the aqueous phase. A variety of dithiophosphonate salts was obtained from stable 2,4-diary1- and 2,4-diferrocenyl-1,3- dithiadiphosphetane disulfide precursors, []. The fo...
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
1998.
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| Subjects: | |
| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=733061961&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | characterization of new dithiophosphonate salts and their capacity to facilitate metal complex formation both in the organic and the aqueous phase. A variety of dithiophosphonate salts was obtained from stable 2,4-diary1- and 2,4-diferrocenyl-1,3- dithiadiphosphetane disulfide precursors, []. The formation and characterization of binuclear gold(I) dithiophosphinate complexes of the type [] are described. These complexes show both the presence (R = Ph) and absence (R = Et) of intermolecular [] interactions in the solid state. Reaction between [] and [] leads to three-coordinate Au(1) complexes with molecular formula []. Reaction between [] and [] in [] leads to the mixed ligand complex [] in high yield. The latter complex reacts with [] to form the oxidative addition product [], the first gold(I) complex with a S-P-S bridging moiety. The X-ray crystal structure of both these complexes exhibit rare boat conformations and the latter has a formal Au(II)- Au(II) single bond. The formation, characterization, reactivity pathways and luminescence properties of binuclear gold(I) dithiophosphonate complexes of the type [] comprise the bulk of this study. These complexes are formed in satisfactory yield from the reaction between [] (THT = tetrahydrothiophene) and [] salts in THF at ambient temperature. Five single crystal X- ray structures of the complexes [] were determined. These complexes all crystallize as the trams isomer in an elongated chair conformation. Among the complexes investigated, structural types were found where intermolecular [] interactions (-2.90 - 3.20 Ø) were present and absent. [] and [] studie reveal both the cis and trams isomers are present ins solution. The reaction between [] and [] in THF leads to the formation of new heterobridged trithiophosphonate gold(I) complexes of the type []. The cationic complex [] is formed and isolated from the ligand transfer reaction between [] and []. The luminescence properties of several structurally characterized complexes were investigated. A correlation between the emission profile and the presence of weak intermolecular [] interactions in the solid state was established, The mononuclear copper(I) complex [] was isolated and structurally characterized. The formation of several tris-chelate octahedral iron(III) complexes of the type [] was isolated from the aqueous phase and characterized. |
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| Item Description: | Vita. "Major Subject: Chemistry". |
| Physical Description: | xiii, 142 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilm Inc. |
| Bibliography: | Includes bibliographical references (leaves 115-127). |