Tuning diastereoisomerism in platinum(II) phosphino- and aminothiolato hydrido complexes
dc.contributor.author
dc.date.accessioned
2017-04-19T11:27:05Z
dc.date.available
2017-04-19T11:27:05Z
dc.date.issued
2017-03-06
dc.identifier.issn
1144-0546
dc.identifier.uri
dc.description.abstract
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-κP) thiolato-κS] 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-κN) thiolato-κS] 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-κP) thiolato-κS] 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)
dc.description.sponsorship
We thank the Spanish Ministerio de Economía y Competitividad (MINECO) for projects BQU2002-04070-C02-01, CTQ2014-54306-P and CTQ2014-59832-JIN. This work has also been supported by the Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia 2014 prize for M. S.)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
MICYT/PN 2002-2005/BQU2002-04070-C02-01
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/C6NJ04042J
dc.relation.ispartof
New Journal of Chemistry, 2017,vol. 41, p. 3015-3028
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Attribution 3.0 Spain
dc.rights.uri
dc.subject
dc.title
Tuning diastereoisomerism in platinum(II) phosphino- and aminothiolato hydrido complexes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
026748
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1369-9261