A ZWITTERIONIC MONOALKYLATED DERIVATIVE OF [Pt2(µ-S)2(PPh3)4] FROM 1,3-PROPANESULTONE

platinum complex alkylation reaction zwitterions thiolate ligand X-ray crystal structure

ИДЕНТИФИКАЦИЯ ПРОДУКТОВ ОРГАНИЧЕСКИХ РЕАКЦИЙ ПРИ ОТСУТСТВИИ АДДИТИВНОСТИ ХРОМАТОГРАФИЧЕСКИХ ИНДЕКСОВ УДЕРЖИВАНИЯ. ХЛОРПРОИЗВОДНЫЕ МЕТИЛ-трет-БУТИЛКЕТОНА, CRYSTAL STRUCTURES OF new ISOSTRUCTURAL OXOVANADIUM(V) COMPLEXES WITH HYDRAZONE LIGANDS, ...

The dinuclear platinum(II) sulfido complex [Pt2(-S)2(PPh3)4] 1 has been known for many years to contain highly nucleophilic sulfide centers [ 1 ]. <...> This reactivity can be harnessed in the assembly of multi-metallic sulfide-bridged aggregates [ 2—5 ] or alternatively alkyl- or aryl-thiolate ligands can be generated by alkylation [ 6—11 ] or arylation [ 12, 13 ] reactions using suitable electrophiles. <...> In recent years we have been exploiting this reactivity using electrospray ionisation mass spectrometry [ 14 ] which offers advantages in terms of efficiency and simplicity [ 15 ]. <...> The vast majority of such alkylated and arylated derivatives are cationic, with counteranions (such as PF6 or BPh4 ) added to effect precipitation and isolation of the complexes. <...> In this contribution we report investigations into the synthesis and characterization of a novel zwitterionic alkylated derivative of [Pt2(-S)2(PPh3)4], formed by alkylation with 1,3-propanesultone 2 (a well-known alkylating agent [ 16 ]) giving a product where the resulting sulfonate (—SO3 ) counterion is retained as part of the alkylthiolate group. <...> Additional 0.66 mmol portions of sultone were added after 5 and 16 hours stirring. <...> Structures were solved by the direct methods option of SHELXS-97 [ 20 ] and the Pt, S and P atoms were located. <...> The consequential disorder of the SO3 group could not be resolved for S(3), O(1), and O(2) where it appeared as elongated ellipsoids, but O(3) could be split into two components. <...> Two molecules of CH2Cl2 were apparent, one ordered and one disordered over three orientations. <...> Two significant residual peaks were assigned as a fully occupied H2O site, hydrogen bonding between an SO3 O atom and the nonalkylated S atom, and the other a half-occupied H2O site associated with disordered CH2Cl2. <...> In the final refinement cycles, non-H atoms were assigned anisotropic temperature factors while the C atoms of disordered CH2Cl2, the disordered propyl chain C atoms, and the O atoms were treated isotropically. <...> RESULTS AND DISCUSSION The reaction of [Pt2(-S)2(PPh3)4] 1 with excess 1,3-propanesultone 2 was carried out in methanol suspension, resulting in alkylation of one of the sulfide centers <...>

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