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

作者：Ujam Oguejiofo T; Devoy Sarah M; Henderson William^*; Nicholson Brian K; Hor T S Andy

来源：Dalton Transactions, 2012, 41(41): 12773-12780.

DOI：10.1039/c2dt31637d

Reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with the dialkylating agents ClCH2C(O)CH2Cl or ClCH2C(=NNHC(O)NH2)CH2Cl gives the dicationic di-mu-thiolate complexes [Pt-2{mu-SCH2C(O)CH2S)(PPh3)(4)](2+) or [Pt-2{mu-SCH2C(=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 [Pt-2{mu-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 [Pt-2(mu-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 (1)J(PtP) coupling constant to the trans PPh3 ligand. Reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with the 2,4-dinitrophenyl-hydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt-2{mu-SCH2C-(=NNHAr)CHS}(PPh3)(3)Cl] [Ar = C6H3(NO2)(2)] in which a PPh3 ligand is substituted by a chloride.

• 出版日期2012