Journal of the American Chemical Society, Vol.129, No.15, 4551-4566, 2007
Alkylthio bridged 44 cve triangular platinum clusters: Synthesis, oxidation, degradation, ligand substitution, and quantum chemical calculations
Acetylplatinum(II) complexes trans-[Pt(COMe)Cl(L)(2)] (L = PPh3, 2a; P(4-FC6H4)(3), 2b) were found to react with dialkyldisulfides R2S2 (R = Me, Et, Pr, Bu; Pr = n-propyl, Bu = n-butyl), yielding trinuclear 44 cve (cluster valence electrons) platinum clusters [(PtL)(3)(mu-SR)(3)]Cl (4). The analogous reaction of 2a-b with Ph2S2 gave SPh bridged dinuclear complexes trans-[{PtCl(L)}(2)(mu-SPh)(2)] (5), whereas the addition of Bn2S2 (Bn = benzyl) to 2a ended up in the formation of [{Pt(PPh3)}(3)(mu(3)-S)(mu-SBn)(3)]Cl (6). Theoretical studies based on the AIM theory revealed that type 4 complexes must be regarded as triangular platinum clusters with Pt-Pt bonds whereas complex 6 must be treated as a sulfur capped 48 ve (valence electrons) trinuclear platinum(II) complex without Pt-Pt bonding interactions. Phosphine ligands with a lower donor capability in clusters 4 proved to be subject to substitution by stronger donating monodentate phosphine ligands (L' = PMePh2, PMe2Ph, PBu3) yielding clusters [(PtL')(3)(mu-SR)(3)]Cl (9). In case of the reaction of clusters 4 and 9 with PPh2CH2PPh2 (dppm), a fragmentation reaction occurred, and the complexes [(PtL)(2)(mu-SMe)(mu-dppm)]Cl (12) and [Pt(mu-SMe)(2)(dppm)] (13) were isolated. Furthermore, oxidation reactions of cluster [{Pt(PPh3)}(3)(mu-SMe)(3)]Cl (4a) using halogens (Br-2, I-2) gave dimeric platinum(II) complexes cis-[{PtX(PPh3)}(2)(mu-SMe)(2)] (14, X = Br, I) whereas oxidation reactions using sulfur and selenium afforded chalcogen capped trinuclear 48 ve complexes [{Pt(PPh3)}(3)(mu(3)-E)(mu-SMe)(3)] (15, E = S, Se). All compounds were fully characterized by means of NMR and IR spectroscopy, microanalyses, and ESI mass spectrometry. Furthermore, X-ray diffraction analyses were performed for the triangular cluster 4a, the trinuclear complex 6, as well as for the dinuclear complexes trans-[{Pt(AsPh3)}(2)(mu-SPh)(2)] (5c), [{Pt(PPh3)}(2)(mu-SMe)(mu-dppm)]Cl (12a), and [{{PtBr(PPh3)}(2)(mu-SMe)(2)] (14a).