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https://scholarbank.nus.edu.sg/handle/10635/15814
DC Field | Value | |
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dc.title | Synthesis and reactivity of group 6 and group 8 organometallic complexes with sulfur-containing ligands | |
dc.contributor.author | KUAN SEAH LING | |
dc.date.accessioned | 2010-04-08T10:57:43Z | |
dc.date.available | 2010-04-08T10:57:43Z | |
dc.date.issued | 2009-03-25 | |
dc.identifier.citation | KUAN SEAH LING (2009-03-25). Synthesis and reactivity of group 6 and group 8 organometallic complexes with sulfur-containing ligands. ScholarBank@NUS Repository. | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/15814 | |
dc.description.abstract | The reactions of the scorpionate salts, K[HB(mt)3], Na[H2B(mt)2] and Li[HB(mt)2(pz)] with the organometallic complexes, [Cp*CrBr2]2 (1), [(HMB)RuIICl2]2 (8), [Cp*RuIIICl2]2 (12) and [Cp*RuII(OMe)]2 (13) yielding Cp*CrIII, (HMB)RuII and Cp*RuII/III complexes containing poly(methimazolyl)borates are described. The coordination modes of these ligands to the metal centres were determined using X-ray structural, electrochemical or/and NMR spectroscopic studies.The one-electron electrochemical oxidation of [Cp*RuIVCl2(S2CR)] (21-22) give [Cp*RuVCl2(S2CR)]+ (21+-22+). These complexes contain Ru in the most highly oxidized state ever recorded in organometallic chemistry. On the other hand, the chemical oxidation of [Cp*RuIVCl2(S2CNMe2)] (21a) with NOPF6 and [(C6H4Br)3N](SbCl6) gave the Ru(IV) complexes, [Cp*RuIV(MeCN)2(S2CNMe)](PF6)2 (23) and [Cp*RuIV(S2CNMe2)]2(SbCl6)2 (24). The reactions of [Cpb Ru(CO)2] (Cpb =C5H5, 25a; Cpb =C5Me5, 25b) with the heterocyclic disulfides lead to the isolation of the complexes of the type, [Cpb Ru(CO)B,2(o +1-SR)] (26-29) in moderate to high yields. IR spectroscopic, electrochemical and crystallographic studies have shown that the electron donating ability of SPy>SBzt>SPyCOOH>SBzCOOH. Complexes 26 and 27 were found to exhibit antiproliferative activity against MDA-MB231 and MCF-7 breast cancer cell lines and it was observed that the toxicity increased in order of increasing electron-donating ability of the ligands. In addition, the reactivity of 25 towards henb s egg white lysozyme (HEWL) was investigated and 25a was found to cleave two out of the four disulfide bonds present in the protein, HEWL. | |
dc.language.iso | en | |
dc.subject | poly(methimazolyl)borates, heterocyclic thiols, ruthenium, electrochemistry | |
dc.type | Thesis | |
dc.contributor.department | CHEMISTRY | |
dc.description.degree | Ph.D | |
dc.description.degreeconferred | DOCTOR OF PHILOSOPHY | |
dc.identifier.isiut | NOT_IN_WOS | |
Appears in Collections: | Ph.D Theses (Open) |
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