Electrochemistry, protein binding and crystal structures of platinum(II) and platinum(IV) carboxylato complexes

Andrew R. Battle; Glen B. Deacon; Rachael C. Dolman; Trevor W. Hambley

doi:10.1071/CH02086

Electrochemistry, protein binding and crystal structures of platinum(II) and platinum(IV) carboxylato complexes

Andrew R. Battle, Glen B. Deacon, Rachael C. Dolman, Trevor W. Hambley

School of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

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Abstract

The crystal structures of the platinum(II) complexes [Pt(ox)(en)] (ox = oxalato, en = ethane-1,2-diamine) and [Pt(ethmal)(en)] (ethmal = ethylmalonato), and of their platinum(IV) analogues, trans-[Pt(OH)₂(ox)(en)].H₂O and trans-[Pt(ethmal)(OH)₂(en)], have been determined. All crystallize in the monoclinic space group P2₁/c, with the exception of trans-[pt^IV(OH)₂(ox)(en)].H₂O which crystallizes in C2/c. The ethylmalonato ligand in [Pt^II(ethmal)(en)] adopts a pseudo-boat conformation. Changes in the fold angles of the boat occur on oxidation and introduction of the trans hydroxo ligands. The cathodic forward half-wave potentials of the platinum(IV) complexes (including trans-[Pt(mal)(OH)₂(en)], mal= malonato) are reported and reveal that these complexes are more difficult to reduce than analogous complexes with equatorial chloro ligands. The binding of trans-[Pt(OH)₂(ox)(en)].H₂O and trans-[Pt(mal)(OH)₂(en)] to mouse albumin was investigated with no binding observed after 6 h and a very small amount observed for the latter complex after 24 h.

Original language	English
Pages (from-to)	699-704
Number of pages	6
Journal	Australian Journal of Chemistry
Volume	55
Issue number	11
DOIs	https://doi.org/10.1071/CH02086
Publication status	Published - 1 Dec 2002

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title = "Electrochemistry, protein binding and crystal structures of platinum(II) and platinum(IV) carboxylato complexes",

abstract = "The crystal structures of the platinum(II) complexes [Pt(ox)(en)] (ox = oxalato, en = ethane-1,2-diamine) and [Pt(ethmal)(en)] (ethmal = ethylmalonato), and of their platinum(IV) analogues, trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(ethmal)(OH)2(en)], have been determined. All crystallize in the monoclinic space group P21/c, with the exception of trans-[ptIV(OH)2(ox)(en)].H2O which crystallizes in C2/c. The ethylmalonato ligand in [PtII(ethmal)(en)] adopts a pseudo-boat conformation. Changes in the fold angles of the boat occur on oxidation and introduction of the trans hydroxo ligands. The cathodic forward half-wave potentials of the platinum(IV) complexes (including trans-[Pt(mal)(OH)2(en)], mal= malonato) are reported and reveal that these complexes are more difficult to reduce than analogous complexes with equatorial chloro ligands. The binding of trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(mal)(OH)2(en)] to mouse albumin was investigated with no binding observed after 6 h and a very small amount observed for the latter complex after 24 h.",

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N2 - The crystal structures of the platinum(II) complexes [Pt(ox)(en)] (ox = oxalato, en = ethane-1,2-diamine) and [Pt(ethmal)(en)] (ethmal = ethylmalonato), and of their platinum(IV) analogues, trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(ethmal)(OH)2(en)], have been determined. All crystallize in the monoclinic space group P21/c, with the exception of trans-[ptIV(OH)2(ox)(en)].H2O which crystallizes in C2/c. The ethylmalonato ligand in [PtII(ethmal)(en)] adopts a pseudo-boat conformation. Changes in the fold angles of the boat occur on oxidation and introduction of the trans hydroxo ligands. The cathodic forward half-wave potentials of the platinum(IV) complexes (including trans-[Pt(mal)(OH)2(en)], mal= malonato) are reported and reveal that these complexes are more difficult to reduce than analogous complexes with equatorial chloro ligands. The binding of trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(mal)(OH)2(en)] to mouse albumin was investigated with no binding observed after 6 h and a very small amount observed for the latter complex after 24 h.

AB - The crystal structures of the platinum(II) complexes [Pt(ox)(en)] (ox = oxalato, en = ethane-1,2-diamine) and [Pt(ethmal)(en)] (ethmal = ethylmalonato), and of their platinum(IV) analogues, trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(ethmal)(OH)2(en)], have been determined. All crystallize in the monoclinic space group P21/c, with the exception of trans-[ptIV(OH)2(ox)(en)].H2O which crystallizes in C2/c. The ethylmalonato ligand in [PtII(ethmal)(en)] adopts a pseudo-boat conformation. Changes in the fold angles of the boat occur on oxidation and introduction of the trans hydroxo ligands. The cathodic forward half-wave potentials of the platinum(IV) complexes (including trans-[Pt(mal)(OH)2(en)], mal= malonato) are reported and reveal that these complexes are more difficult to reduce than analogous complexes with equatorial chloro ligands. The binding of trans-[Pt(OH)2(ox)(en)].H2O and trans-[Pt(mal)(OH)2(en)] to mouse albumin was investigated with no binding observed after 6 h and a very small amount observed for the latter complex after 24 h.

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Electrochemistry, protein binding and crystal structures of platinum(II) and platinum(IV) carboxylato complexes

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