Faculté des sciences

Asymmetric Synthesis of Coordination Compounds: Back to the Roots. Diastereoselective Synthesis of Simple Platinum(IV) Complexes

Drahoňovský, Dušan ; Zelewsky, Alexander von

In: Helvetica Chimica Acta, 2005, vol. 88(3), p. 496-506

A publication by Alexander P. Smirnoff in Helvetica Chimica Acta in 1920 [6] describes the first synthesis of a coordination species, i.e., of tris(propane-1,2-diamine-κN¹,κN²)platinum(4+) ([PtIV(pn)₃]⁴⁺), where it was shown that the configuration of a chiral center in the ligand can influence the configuration at the metal. The present investigation of... More

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    Summary
    A publication by Alexander P. Smirnoff in Helvetica Chimica Acta in 1920 [6] describes the first synthesis of a coordination species, i.e., of tris(propane-1,2-diamine-κN¹,κN²)platinum(4+) ([PtIV(pn)₃]⁴⁺), where it was shown that the configuration of a chiral center in the ligand can influence the configuration at the metal. The present investigation of [PtIV(pn)₃]⁴⁺ was carried out by NMR spectroscopy, where all nuclei in the metal complex were used as sources of information, i.e., ¹H, ¹³C, ¹⁵N, and ¹⁹⁵Pt. ¹³C-NMR and ¹⁵N-NMR spectroscopy (of isotopically enriched complex) were especially informative for the analysis of isomer distribution. Stereoselectivity in the formation reaction of the complexes is rather modest, whereas Δ-, and Λ-isomers can be separated efficiently by crystallization. A mixture of [Pt{(S)-pn}₃]⁴⁺ and [Pt{(R)-pn}₃]⁴⁺ shows no scrambling of the enantiomeric ligands, thus proving the inertness of the complexes.