Tris(phenylthiomethyl)phosphane Sulfide and Selenide, (PhSCH2)3PX (X = S, Se), as Ambidentate Ligand Systems in Copper(I) Complexes
✍ Scribed by Fuchs, Stefan ;Angermaier, Klaus ;Bauer, Andreas ;Schmidbaur, Hubert
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1997
- Tongue
- English
- Weight
- 628 KB
- Volume
- 130
- Category
- Article
- ISSN
- 0009-2940
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✦ Synopsis
Triphenylphosphite has been converted into tris(pheny1thio-methy1)phosphane (1) by reaction with LiCH2SPh/DABC0, and subsequently into the corresponding sulfide (2) and selenide (3) by treatment with elemental sulfur or selenium, respectively. Ligands 2 and 3 react with copper(1) halides CuX (X = C1, Br, I) in polar organic solvents to give either 1 : 1 (X = C1: 4, 7, X = Br: 5 , 8 ) or 1:2 complexes (X = Br: 9, X = I: 6, 10). The crystal structures of five of these complexes have been determined by single crystal X-ray diffraction studies. All compounds of the type [(PhSCH2)3P=S/Se]CuX (X = C1, Br) form centrosymmetrical dinuclear complexes featuring a four-membered ring core Cu2[S/Se], fused to two five-membered rings Cu[S/Se]PCS through common trans edges. Only one of the three phenyl-thiomethyl functions is involved in coordination to a metal center. The compound (PhSCH,),%P=S, ( 6) is associated into a centrosymmetrical tetranuclear complex containing two four-membered rings (ICu2S) bridged via iodine atoms in 1 . 3 4 s positions. The ligand is found to employ two of its PhSCH, functions for metal coordination, giving rise to two five-membered rings fused to the four-membered rings via neighbouring edges. In all cases, therefore, the P=S/Se functions of the ligands are the preferred donor sites, which are used for the building of bridgehead structural units of polynuclear complexes.