Tuning diastereoisomerism in platinum(ii) phosphino- and aminothiolato hydrido complexes. (20th March 2017)

• Record Type: Journal Article
• Authors: Polo, A.; Duran, J.; Juanola, R.; Real, J.; Benet-Buchholz, J.; Solà, M.; Poater, A.
• Is Part Of: New journal of chemistry. Volume 41:Number 8(2017)
• Page Start: 3015
• Page End: 3028
• Publication Date: 2017-03-20
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c6nj04042j
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Tuning between the cis and trans Pt(ii ) based complexes bearing phosphinothiolato and aminothiolato ligands. Abstract : Chelate assisted oxidative addition of one equivalent of 2-phosphinothiols (2-(diphenylphosphino)ethanethiol1, 1-(benzyloxy)-2-(diphenylphosphino)ethanethiol2 and 2-(diphenylphosphino)-cyclohexanethiol3 ) to tetrakis(triphenylphosphine)platinum(0) gives the corresponding hydrido[2-(phosphino-κ P )thiolato-κ S ]triphenylphosphineplatinum(ii ) complexes8–10 . 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 of8 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 ) complexes5–7 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)propanethiol4 to tetrakis(triphenylphosphine)platinum(0) gives the resultant hydrido[3-(phosphino-κ P )thiolato-κ S ]triphenylphosphineplatinum(ii ) complex11 . 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 ).