Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/23168
Title: Reactivities and template syntheses of / on the {Pt2S2} core towards organic electrophiles
Authors: CHONG SIEW HUAY
Keywords: Platinum, sulfide, thiolate, nucleophilic, alkylation, pressure,
Issue Date: 14-Sep-2007
Source: CHONG SIEW HUAY (2007-09-14). Reactivities and template syntheses of / on the {Pt2S2} core towards organic electrophiles. ScholarBank@NUS Repository.
Abstract: A comprehensive study on the alkylation reactions of the bridging sulfido ligands in platinum complexes containing the {Pt2(A?-S)2} core is presented. By reacting [Pt2(A?-S)2(P-P)2] (P-P = 2PPh3 and dppp) with various organic electrophiles, a series of structurally and chemically diverse functional groups (R) is appended onto the sulfide centers. In doing so, a straightforward methodology of using a metal sulfide template to novel A?-thiolate ligands and organosulfur materials becomes accessible. Electrospray ionization mass spectrometry assists the study of the above transformations. A major outcome is the isolation of stable dialkylated complexes of the types, [Pt2(I?-S2R)(P-P)2](PF6)2, [Pt2(I?-SR)2(P-P)2](PF6)2 and [Pt2(A?-SR)(A?-SRa??)(P-P)2](PF6)2 (Ra? Ra??). Prior to this, dialkylation remains elusive due to the deactivation of the unsubstituted sulfur or the disintegration of the {Pt2(A?-S)2} core. Intermolecular alkylation interlinks two {Pt2(A?-S)2} moieties to give Pt4 aggregates, [(PPh3)4Pt2(I?-S)(I?-SRS)(I?-S)Pt2(PPh3)4](PF6)2. The use of pressure to facilitate difficult alkylations and hence resulting in the liberation of a dithiacyclophane will also be highlighted.
URI: http://scholarbank.nus.edu.sg/handle/10635/23168
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02 thesis content page Chong SH.pdf106.17 kBAdobe PDF

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03 acknowledgement _summary_declaration_lists of_Chong SH.pdf417.3 kBAdobe PDF

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04 Chapter 1_Chong SH.pdf659.59 kBAdobe PDF

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05 Chapter 2 Chong SH.pdf1.4 MBAdobe PDF

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