Please use this identifier to cite or link to this item: https://doi.org/10.1016/j.ica.2009.10.005
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
Authors: Devoy, S.M.
Henderson, W.
Nicholson, B.K.
Hor, T.S.A. 
Keywords: Alkylation reactions
Crystal structures
Electrospray mass spectrometry
Platinum complexes
Sulfide complexes
Thiolate complexes
Issue Date: 4-Jan-2010
Source: Devoy, S.M., Henderson, W., Nicholson, B.K., Hor, T.S.A. (2010-01-04). 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. ScholarBank@NUS Repository. https://doi.org/10.1016/j.ica.2009.10.005
Abstract: The 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.
Source Title: Inorganica Chimica Acta
URI: http://scholarbank.nus.edu.sg/handle/10635/94046
ISSN: 00201693
DOI: 10.1016/j.ica.2009.10.005
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