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

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