File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: A novel structural rearrangement reaction of dialkylated derivatives of [Pt 2(μ-S) 2(PPh 3) 4] involving Pt-C bond formation

TitleA novel structural rearrangement reaction of dialkylated derivatives of [Pt 2(μ-S) 2(PPh 3) 4] involving Pt-C bond formation
Authors
Issue Date2012
Citation
Dalton Transactions, 2012, v. 41, n. 41, p. 12773-12780 How to Cite?
AbstractReaction of [Pt 2(μ-S) 2(PPh 3) 4] with the dialkylating agents ClCH 2C(O)CH 2Cl or ClCH 2C(NNHC(O)NH 2)CH 2Cl gives the dicationic di-μ-thiolate complexes [Pt 2{μ-SCH 2C(O)CH 2S)(PPh 3) 4] 2+ or [Pt 2{μ-SCH 2C(NNHC(O)NH 2)CH 2S} (PPh 3) 4] 2+, isolated as BPh 4 - salts and characterised by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray crystallography. Treatment of the complex [Pt 2{μ-SCH 2C(O)CH 2S)(PPh 3) 4] 2+, which contains a [6.6.4] bicyclic system, with hydroxide ions results in deprotonation of a CH 2 group and rearrangement of the resulting monocation, giving [Pt 2(μ-SCH 2C(O)CHS}(PPh 3) 4] +, isolated as its PF 6 - salt. An X-ray structure determination shows the complex to have a novel rearranged [6.5.5] bicyclic system containing a Pt-S-Pt-S-C five-membered ring with a Pt-C bond. The alkyl ligand has a high trans-influence, manifest in a long trans Pt-P bond and small 1J(PtP) coupling constant to the trans PPh 3 ligand. Reaction of [Pt 2(μ-S) 2(PPh 3) 4] with the 2,4-dinitrophenylhydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt 2{μ-SCH 2C(NNHAr)CHS} (PPh 3) 3Cl] [Ar = C 6H 3(NO 2) 2] in which a PPh 3 ligand is substituted by a chloride. © 2012 The Royal Society of Chemistry.
Persistent Identifierhttp://hdl.handle.net/10722/219675
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404

 

DC FieldValueLanguage
dc.contributor.authorUjam, Oguejiofo T.-
dc.contributor.authorDevoy, Sarah M.-
dc.contributor.authorHenderson, William-
dc.contributor.authorNicholson, Brian K.-
dc.contributor.authorHor, T. S Andy-
dc.date.accessioned2015-09-23T02:57:41Z-
dc.date.available2015-09-23T02:57:41Z-
dc.date.issued2012-
dc.identifier.citationDalton Transactions, 2012, v. 41, n. 41, p. 12773-12780-
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10722/219675-
dc.description.abstractReaction of [Pt 2(μ-S) 2(PPh 3) 4] with the dialkylating agents ClCH 2C(O)CH 2Cl or ClCH 2C(NNHC(O)NH 2)CH 2Cl gives the dicationic di-μ-thiolate complexes [Pt 2{μ-SCH 2C(O)CH 2S)(PPh 3) 4] 2+ or [Pt 2{μ-SCH 2C(NNHC(O)NH 2)CH 2S} (PPh 3) 4] 2+, isolated as BPh 4 - salts and characterised by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray crystallography. Treatment of the complex [Pt 2{μ-SCH 2C(O)CH 2S)(PPh 3) 4] 2+, which contains a [6.6.4] bicyclic system, with hydroxide ions results in deprotonation of a CH 2 group and rearrangement of the resulting monocation, giving [Pt 2(μ-SCH 2C(O)CHS}(PPh 3) 4] +, isolated as its PF 6 - salt. An X-ray structure determination shows the complex to have a novel rearranged [6.5.5] bicyclic system containing a Pt-S-Pt-S-C five-membered ring with a Pt-C bond. The alkyl ligand has a high trans-influence, manifest in a long trans Pt-P bond and small 1J(PtP) coupling constant to the trans PPh 3 ligand. Reaction of [Pt 2(μ-S) 2(PPh 3) 4] with the 2,4-dinitrophenylhydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt 2{μ-SCH 2C(NNHAr)CHS} (PPh 3) 3Cl] [Ar = C 6H 3(NO 2) 2] in which a PPh 3 ligand is substituted by a chloride. © 2012 The Royal Society of Chemistry.-
dc.languageeng-
dc.relation.ispartofDalton Transactions-
dc.titleA novel structural rearrangement reaction of dialkylated derivatives of [Pt 2(μ-S) 2(PPh 3) 4] involving Pt-C bond formation-
dc.typeArticle-
dc.description.natureLink_to_subscribed_fulltext-
dc.identifier.doi10.1039/c2dt31637d-
dc.identifier.scopuseid_2-s2.0-84867298905-
dc.identifier.volume41-
dc.identifier.issue41-
dc.identifier.spage12773-
dc.identifier.epage12780-
dc.identifier.eissn1477-9234-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats