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dc.contributor.authorThirumoorthi, Ramalingam
dc.contributor.authorChivers, Tristram
dc.contributor.authorHäggman, Susanna
dc.contributor.authorMansikkamäki, Akseli
dc.contributor.authorMorgan, Ian
dc.contributor.authorTuononen, Heikki
dc.contributor.authorLahtinen, Manu
dc.contributor.authorKonu, Jari
dc.date.accessioned2016-08-31T10:59:31Z
dc.date.available2017-07-19T21:45:06Z
dc.date.issued2016
dc.identifier.citationThirumoorthi, R., Chivers, T., Häggman, S., Mansikkamäki, A., Morgan, I., Tuononen, H., Lahtinen, M., & Konu, J. (2016). Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]-: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes. <i>Dalton Transactions</i>, <i>45</i>(32), 12691-12701. <a href="https://doi.org/10.1039/c6dt02565j" target="_blank">https://doi.org/10.1039/c6dt02565j</a>
dc.identifier.otherCONVID_26134824
dc.identifier.otherTUTKAID_70751
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/51144
dc.description.abstractA high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn–S(C) and Zn–S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(II) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S′,S′′) mode to the Ni(II) centre with three distinctly different Ni–S bond lengths (2.3487(8), 2.4500(9) and 2.5953(10) Å). By contrast, in the red-brown square-planar complex 5b the two ligands are S,S′-chelated to Ni(II) (d(Ni–S) = 2.165(2) and 2.195(2) Å) with one pendant PPh2S group. DFT calculations revealed that the energetic difference between singlet and triplet state octahedral and square-planar isomers of the Ni(II) complex is essentially indistinguishable. Consistently, VT and 31P CP/MAS NMR spectroscopic investigations indicated that a mixture of isomers exists in solution at room temperature, while the singlet state square-planar isomer 5b becomes favoured at −40 °C.
dc.language.isoeng
dc.publisherRSC Publications
dc.relation.ispartofseriesDalton Transactions
dc.subject.otherrikkipohjaiset ligandit
dc.subject.othermetallikompleksit
dc.subject.otherelektronirakenteet
dc.subject.otherisomerisaatio
dc.subject.othersulphur-centered ligands
dc.subject.othermetal complexes
dc.subject.otherelectronic structures
dc.subject.otherisomerization
dc.titleSynthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]-: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201608303916
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2016-08-30T12:15:10Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange12691-12701
dc.relation.issn1477-9226
dc.relation.numberinseries32
dc.relation.volume45
dc.type.versionacceptedVersion
dc.rights.copyright© The Royal Society of Chemistry 2016. This is a final draft version of an article whose final and definitive form has been published by RSC. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1039/c6dt02565j
dc.type.okmA1


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