Investigations of the chemistry of platinum(II) amine complexes

Barnham, Kevin Jeffrey (1993). Investigations of the chemistry of platinum(II) amine complexes PhD Thesis, School of Molecular and Microbial Sciences, University of Queensland. doi:10.14264/uql.2016.432

       
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Author Barnham, Kevin Jeffrey
Thesis Title Investigations of the chemistry of platinum(II) amine complexes
School, Centre or Institute School of Molecular and Microbial Sciences
Institution University of Queensland
DOI 10.14264/uql.2016.432
Publication date 1993
Thesis type PhD Thesis
Supervisor Trevor Appleton
Total pages 183
Language eng
Subjects 06 Biological Sciences
Formatted abstract
Multinuclear MR has been used to probe the chemistry of the cis- and trans-diammineplatinum(II) moiety. A convenient method for the small scale preparation of trans-PtCl2(NH3)2 has been devised which involves heating solid [Pt(NH3)4]Cl2 at 190 - 195°C under vacuum for approximately 5 hours. The chloro ligands were removed by heating an aqueous suspension of trans-PtCl2(NH3)2 with AgNO3 at 90°C for 48 hours under a N2 atmosphere. The aqueous solution chemistry of trans-diammineplatinum(II) complexes with aqua, hydroxo, chloro, nitrato, sulfato, acetato, and phosphato ligands, was also investigated, with 15N and 195Pt NMR spectroscopy used to characterise species in solution. 

The interactions of the trans-diammineplatinum(II) moiety with sulfur containing amino acids were investigated in aqueous solution . The reaction between trans-PtCl2(NH3)2(H20)22+ and sulfhydryl amino acids was dependent on pH. The reaction of trans-PtCl2(NH3)2(H20)22+ with H3accys was used as a model for reactions of thiols, with glutathione behaving in an identical fashion. At high pH (> 8) trans-PtCl2(NH3)2 reacted with H3accys slowly to give trans-Pt(H2accys)(OH)(NH3)2 and then trans-Pt(H2accys)2(NH3)2. At intermediate pH (5-7) another species was formed, trans-[{Pt(H2accys)(NH3)2}2(µ-H2accys)]+. At lower pH values (<4) further bridging by the thiol sulfur occured and coordinated ammine was liberated. A polymeric solid also formed at low pH. trans-PtCl2(NH3)2(H20)22+ formed polymeric solids at low pH with cys, homocys, H3accys, and glutathione.   .................................................................
Keyword Platinum compounds

Document type: Thesis
Collection: UQ Theses (RHD) - UQ staff and students only
 
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