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Article: Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

TitleTuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]
Authors
KeywordsCrystal structures
Electrospray mass spectrometry
Lead complexes
Platinum complexes
Sulfide ligands
Issue Date2007
Citation
Journal of Organometallic Chemistry, 2007, v. 692, n. 22, p. 4933-4942 How to Cite?
AbstractReactions of [Pt2(μ-S)2(PPh3)4] with Ph3PbCl, Ph2PbI2, Ph2PbBr2 and Me3PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt2(μ-S)2(PPh3)4PbR3]+ (R3 = Ph3, Ph2I, Ph2Br, Me3) isolated as PF6 - or BPh4 - salts. In the case of the Me3Pb and Et3Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt2(μ-S)(μ-SR)(PPh3)4]+ (R = Me, Et). X-ray structure determinations on [Pt2(μ-S)2(PPh3)4PbMe3]PF6 and [Pt2(μ-S)2(PPh3)4PbPh2I]PF6 have been carried out, revealing different coordination modes. In the Me3Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph2PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt2S2} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt2(μ-S)2(PPh3)4PbR3]+ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh3 in all cases; for R = Ph, loss of PbPh2 occurs, yielding [Pt2(μ-S)2(PPh3)3Ph]+, while for R = Me, reductive elimination of ethane gives [Pt2(μ-S)2(PPh3)3PbMe]+, which is followed by loss of CH4. © 2007 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/219545
ISSN
2015 Impact Factor: 2.336
2015 SCImago Journal Rankings: 0.732

 

DC FieldValueLanguage
dc.contributor.authorPham, Kristina-
dc.contributor.authorHenderson, William-
dc.contributor.authorNicholson, Brian K.-
dc.contributor.authorHor, T. S Andy-
dc.date.accessioned2015-09-23T02:57:21Z-
dc.date.available2015-09-23T02:57:21Z-
dc.date.issued2007-
dc.identifier.citationJournal of Organometallic Chemistry, 2007, v. 692, n. 22, p. 4933-4942-
dc.identifier.issn0022-328X-
dc.identifier.urihttp://hdl.handle.net/10722/219545-
dc.description.abstractReactions of [Pt2(μ-S)2(PPh3)4] with Ph3PbCl, Ph2PbI2, Ph2PbBr2 and Me3PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt2(μ-S)2(PPh3)4PbR3]+ (R3 = Ph3, Ph2I, Ph2Br, Me3) isolated as PF6 - or BPh4 - salts. In the case of the Me3Pb and Et3Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt2(μ-S)(μ-SR)(PPh3)4]+ (R = Me, Et). X-ray structure determinations on [Pt2(μ-S)2(PPh3)4PbMe3]PF6 and [Pt2(μ-S)2(PPh3)4PbPh2I]PF6 have been carried out, revealing different coordination modes. In the Me3Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph2PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt2S2} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt2(μ-S)2(PPh3)4PbR3]+ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh3 in all cases; for R = Ph, loss of PbPh2 occurs, yielding [Pt2(μ-S)2(PPh3)3Ph]+, while for R = Me, reductive elimination of ethane gives [Pt2(μ-S)2(PPh3)3PbMe]+, which is followed by loss of CH4. © 2007 Elsevier B.V. All rights reserved.-
dc.languageeng-
dc.relation.ispartofJournal of Organometallic Chemistry-
dc.subjectCrystal structures-
dc.subjectElectrospray mass spectrometry-
dc.subjectLead complexes-
dc.subjectPlatinum complexes-
dc.subjectSulfide ligands-
dc.titleTuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]-
dc.typeArticle-
dc.description.natureLink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.jorganchem.2007.07.010-
dc.identifier.scopuseid_2-s2.0-34548792818-
dc.identifier.volume692-
dc.identifier.issue22-
dc.identifier.spage4933-
dc.identifier.epage4942-

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