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Article: Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

TitleInfluence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes
Authors
KeywordsCrystal structures
Thiolate complexes
Electrospray mass spectrometry
Platinum complexes
Sulfide complexes
Alkylation reactions
Issue Date2010
Citation
Inorganica Chimica Acta, 2010, v. 363, n. 1, p. 25-32 How to Cite?
AbstractThe reactions of [Pt2(μ-S)2(PPh3)4] with α,ω-dibromoalkanes Br(CH2)nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ and/or di-alkylated [Pt2(μ-S(CH2)nS}(PPh3)4]2+ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt2(μ-S)2(PPh3)4}2{μ-(CH2)12}]2+ was accessible from the reaction of [Pt2(μ-S)2(PPh3)4] with 0.5 mol equivalents of Br(CH2)12Br. [Pt2(μ-S){μ-S(CH2)4Br}(PPh3)4]+ can be cleanly isolated as its BPh4 - salt, but undergoes facile intramolecular di-alkylation at -18 °C, giving the known species [Pt2(μ-S(CH2)4S}(PPh3)4]2+. The reaction of I(CH2)6I with [Pt2(μ-S)2(PPh3)4] similarly gives [Pt2(μ-S){μ-S(CH2)6I}(PPh3)4]+, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt2(μ-S){μ-S(CH2)5Br}(PPh3)4]BPh4 and [Pt2(μ-S(CH2)5S}(PPh3)4](BPh4)2 are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh3 ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt2(μ-S){μ-S(CH2)n-2CH{double bond, long}CH2}(PPh3)m]+ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr. © 2009 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/219614
ISSN
2015 Impact Factor: 1.918
2015 SCImago Journal Rankings: 0.584

 

DC FieldValueLanguage
dc.contributor.authorDevoy, Sarah M.-
dc.contributor.authorHenderson, William-
dc.contributor.authorNicholson, Brian K.-
dc.contributor.authorHor, T. S Andy-
dc.date.accessioned2015-09-23T02:57:32Z-
dc.date.available2015-09-23T02:57:32Z-
dc.date.issued2010-
dc.identifier.citationInorganica Chimica Acta, 2010, v. 363, n. 1, p. 25-32-
dc.identifier.issn0020-1693-
dc.identifier.urihttp://hdl.handle.net/10722/219614-
dc.description.abstractThe reactions of [Pt2(μ-S)2(PPh3)4] with α,ω-dibromoalkanes Br(CH2)nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ and/or di-alkylated [Pt2(μ-S(CH2)nS}(PPh3)4]2+ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt2(μ-S)2(PPh3)4}2{μ-(CH2)12}]2+ was accessible from the reaction of [Pt2(μ-S)2(PPh3)4] with 0.5 mol equivalents of Br(CH2)12Br. [Pt2(μ-S){μ-S(CH2)4Br}(PPh3)4]+ can be cleanly isolated as its BPh4 - salt, but undergoes facile intramolecular di-alkylation at -18 °C, giving the known species [Pt2(μ-S(CH2)4S}(PPh3)4]2+. The reaction of I(CH2)6I with [Pt2(μ-S)2(PPh3)4] similarly gives [Pt2(μ-S){μ-S(CH2)6I}(PPh3)4]+, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt2(μ-S){μ-S(CH2)5Br}(PPh3)4]BPh4 and [Pt2(μ-S(CH2)5S}(PPh3)4](BPh4)2 are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh3 ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt2(μ-S){μ-S(CH2)n-2CH{double bond, long}CH2}(PPh3)m]+ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr. © 2009 Elsevier B.V. All rights reserved.-
dc.languageeng-
dc.relation.ispartofInorganica Chimica Acta-
dc.subjectCrystal structures-
dc.subjectThiolate complexes-
dc.subjectElectrospray mass spectrometry-
dc.subjectPlatinum complexes-
dc.subjectSulfide complexes-
dc.subjectAlkylation reactions-
dc.titleInfluence of chain length on mono- versus di-alkylation in the reactivity of [Pt2(μ-S)2(PPh3)4] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes-
dc.typeArticle-
dc.description.natureLink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.ica.2009.10.005-
dc.identifier.scopuseid_2-s2.0-70450224241-
dc.identifier.volume363-
dc.identifier.issue1-
dc.identifier.spage25-
dc.identifier.epage32-

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