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- Publisher Website: 10.1016/j.jorganchem.2007.07.010
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Article: Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]
Title | Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4] |
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Authors | |
Keywords | Crystal structures Electrospray mass spectrometry Lead complexes Platinum complexes Sulfide ligands |
Issue Date | 2007 |
Citation | Journal of Organometallic Chemistry, 2007, v. 692, n. 22, p. 4933-4942 How to Cite? |
Abstract | Reactions 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 Identifier | http://hdl.handle.net/10722/219545 |
ISSN | 2023 Impact Factor: 2.1 2023 SCImago Journal Rankings: 0.359 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Pham, Kristina | - |
dc.contributor.author | Henderson, William | - |
dc.contributor.author | Nicholson, Brian K. | - |
dc.contributor.author | Hor, T. S Andy | - |
dc.date.accessioned | 2015-09-23T02:57:21Z | - |
dc.date.available | 2015-09-23T02:57:21Z | - |
dc.date.issued | 2007 | - |
dc.identifier.citation | Journal of Organometallic Chemistry, 2007, v. 692, n. 22, p. 4933-4942 | - |
dc.identifier.issn | 0022-328X | - |
dc.identifier.uri | http://hdl.handle.net/10722/219545 | - |
dc.description.abstract | Reactions 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.language | eng | - |
dc.relation.ispartof | Journal of Organometallic Chemistry | - |
dc.subject | Crystal structures | - |
dc.subject | Electrospray mass spectrometry | - |
dc.subject | Lead complexes | - |
dc.subject | Platinum complexes | - |
dc.subject | Sulfide ligands | - |
dc.title | Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4] | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1016/j.jorganchem.2007.07.010 | - |
dc.identifier.scopus | eid_2-s2.0-34548792818 | - |
dc.identifier.volume | 692 | - |
dc.identifier.issue | 22 | - |
dc.identifier.spage | 4933 | - |
dc.identifier.epage | 4942 | - |
dc.identifier.isi | WOS:000250741200017 | - |
dc.identifier.issnl | 0022-328X | - |