Tuning diastereoisomerism in platinum(ii) phosphino- and aminothiolato hydrido complexesElectronic supplementary information (ESI) available: NMR data for ligand 3 and complexes 9 and 10. Computational details, cartesian coordinates, and crystal data for the XRD structures. CCDC 1501904-1501907. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6nj04042j

• Main Authors: Polo, A, Duran, J, Juanola, R, Real, J, Benet-Buchholz, J, Solà, M, Poater, A
• Format: Article
• Language: English
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/c6nj04042j

Chelate assisted oxidative addition of one equivalent of 2-phosphinothiols (2-(diphenylphosphino)ethanethiol 1 , 1-(benzyloxy)-2-(diphenylphosphino)ethanethiol 2 and 2-(diphenylphosphino)-cyclohexanethiol 3 ) to tetrakis(triphenylphosphine)platinum(0) gives the corresponding hydrido[2-(phosphino-κ P )thiolato-κ S ]triphenylphosphineplatinum( ii ) complexes 8-10 . Temperature variable NMR studies show that these complexes display a chemical equilibrium between the cis-P , P and trans-P , P geometries, strongly displaced toward the trans-P , P configuration (70-90%). XRD studies carried out on crystals of 8 indicate that although the two geometric isomers are present in solution, only the trans-P , P is obtained in the solid state. These results differ from the cis-P , N geometry observed for the related hydrido[2-(amino-κ N )thiolato-κ S ]triphenylphosphineplatinum( ii ) complexes 5-7 in solution. The crystal structures obtained for these aminothiolate hydrides show that the cis-P , N configuration is the only one observed in the solid state. Chelate assisted oxidative addition of one equivalent of 3-(diphenylphosphino)propanethiol 4 to tetrakis(triphenylphosphine)platinum(0) gives the resultant hydrido[3-(phosphino-κ P )thiolato-κ S ]triphenylphosphineplatinum( ii ) complex 11 . This 3-phosphinothiolate hydride shows in solution only a trans-P , P geometry but presents two chelate ring conformational isomers. Density functional theory calculations have been used to explore the ligand-based stereoelectronic effects that are determinant in the different diastereoisomerism observed in these platinum( ii ) hydrides ( 5-11 ). Tuning between the cis and trans Pt( ii ) based complexes bearing phosphinothiolato and aminothiolato ligands.