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
dc.contributor.author | Devoy, Sarah M. | |
dc.contributor.author | Henderson, William | |
dc.contributor.author | Nicholson, Brian K. | |
dc.contributor.author | Hor, T.S. Andy | |
dc.date.accessioned | 2009-11-30T01:05:54Z | |
dc.date.available | 2009-11-30T01:05:54Z | |
dc.date.issued | 2010 | |
dc.description.abstract | The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with a,x-dibromoalkanes Br(CH₂)nBr (n = 4, 5, 6, 8, 12) gave monoalkylated [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 degree 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 x-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=CH₂}(PPh₃)m]⁺ (m = 2 or 3; m – 4), most significant for n = 4, formed by elimination of HBr. | en |
dc.identifier.citation | Devoy, S. M., Henderson, E., Nicholson, B. K., & Hor, T. S. A. (2010). 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. Inorganica Chimica Acta, 363(1), 25-32. | en |
dc.identifier.doi | 10.1016/j.ica.2009.10.005 | en |
dc.identifier.uri | https://hdl.handle.net/10289/3443 | |
dc.language.iso | en | |
dc.publisher | Elsevier | en_NZ |
dc.relation.isPartOf | Inorganica Chimica Acta | en_NZ |
dc.subject | platinum complexes | en |
dc.subject | sulfide complexes | en |
dc.subject | thiolate complexes | en |
dc.subject | alkylation reactions | en |
dc.subject | electrospray mass spectrometry | en |
dc.subject | crystal structures | en |
dc.title | 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 | en |
dc.type | Journal Article | en |
pubs.begin-page | 25 | en_NZ |
pubs.elements-id | 34549 | |
pubs.end-page | 32 | en_NZ |
pubs.issue | 1 | en_NZ |
pubs.volume | 363 | en_NZ |
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