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Issue 41, 2012
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A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

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Abstract

Reaction of [Pt2(μ-S)2(PPh3)4] with the dialkylating agents ClCH2C(O)CH2Cl or ClCH2C([double bond, length as m-dash]NNHC(O)NH2)CH2Cl gives the dicationic di-μ-thiolate complexes [Pt2{μ-SCH2C(O)CH2S)(PPh3)4]2+ or [Pt2{μ-SCH2C([double bond, length as m-dash]NNHC(O)NH2)CH2S}(PPh3)4]2+, isolated as BPh4 salts and characterised by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray crystallography. Treatment of the complex [Pt2{μ-SCH2C(O)CH2S)(PPh3)4]2+, which contains a [6.6.4] bicyclic system, with hydroxide ions results in deprotonation of a CH2 group and rearrangement of the resulting monocation, giving [Pt2(μ-SCH2C(O)CHS}(PPh3)4]+, isolated as its PF6 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 PPh3 ligand. Reaction of [Pt2(μ-S)2(PPh3)4] with the 2,4-dinitrophenylhydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt2{μ-SCH2C([double bond, length as m-dash]NNHAr)CHS}(PPh3)3Cl] [Ar = C6H3(NO2)2] in which a PPh3 ligand is substituted by a chloride.

Graphical abstract: A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

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Publication details

The article was received on 23 Jul 2012, accepted on 04 Sep 2012 and first published on 04 Sep 2012


Article type: Paper
DOI: 10.1039/C2DT31637D
Dalton Trans., 2012,41, 12773-12780

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    A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

    O. T. Ujam, S. M. Devoy, W. Henderson, B. K. Nicholson and T. S. A. Hor, Dalton Trans., 2012, 41, 12773
    DOI: 10.1039/C2DT31637D

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