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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 | Citation: | 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 |
Appears in Collections: | Ph.D Theses (Open) |
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01 thesis title page Chong SH.pdf | 40.16 kB | Adobe PDF | OPEN | None | View/Download | |
02 thesis content page Chong SH.pdf | 106.17 kB | Adobe PDF | OPEN | None | View/Download | |
03 acknowledgement _summary_declaration_lists of_Chong SH.pdf | 417.3 kB | Adobe PDF | OPEN | None | View/Download | |
04 Chapter 1_Chong SH.pdf | 659.59 kB | Adobe PDF | OPEN | None | View/Download | |
05 Chapter 2 Chong SH.pdf | 1.4 MB | Adobe PDF | OPEN | None | View/Download | |
06 Chapter 3 Chong SH.pdf | 593.67 kB | Adobe PDF | OPEN | None | View/Download | |
07 Chapter 4 Chong SH.pdf | 290.64 kB | Adobe PDF | OPEN | None | View/Download | |
08 Chapter 5 Chong SH.pdf | 627.87 kB | Adobe PDF | OPEN | None | View/Download | |
09 Chapter 6 Chong SH.pdf | 797.82 kB | Adobe PDF | OPEN | None | View/Download |
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