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Tuning diastereoisomerism in platinum(II) phosphino- and aminothiolato hydrido complexes

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)

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.)

New Journal of Chemistry, 2017,vol. 41, p. 3015-3028

Royal Society of Chemistry (RSC)

Author: Polo Ortiz, Alfonso
Duran i Carpintero, Josep
Juanola, R.
Real i Obradors, Juli
Benet Buchholz, Jordi
Solà i Puig, Miquel
Poater Teixidor, Albert
Date: 2017 March 6
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)
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.)
Format: application/pdf
ISSN: 1144-0546 (versió paper)
1369-9261 (versió electrònica)
Document access: http://hdl.handle.net/10256/13867
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICYT/PN 2002-2005/BQU2002-04070-C02-01
MINECO/PE 2015-2017/CTQ2014-54306-P
MINECO/PE 2015-2018/CTQ2014-59832-JIN
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/C6NJ04042J
Articles publicats (D-Q)
Is part of: New Journal of Chemistry, 2017,vol. 41, p. 3015-3028
Rights: Attribution 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by/3.0/es/
Subject: Funcional de densitat, Teoria del
Density functionals
Reaccions químiques
Chemical reactions
Metalls de transició -- Compostos
Transition metal compounds
Title: Tuning diastereoisomerism in platinum(II) phosphino- and aminothiolato hydrido complexes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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