Alkylthio Bridged 44 cve Triangular Platinum Clusters: Synthesis, Oxidation, Degradation, Ligand Substitution, and Quantum Chemical Calculations
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- 作者：Christian Albrecht ; Sebastian Schwieger ; Clemens Bruhn ; Christoph Wagner ; Ralph Kluge ; Harry Schmidt ; Dirk Steinborn
- 刊名：Journal of the American Chemical Society
- 出版年：2007
- 出版时间：April 18, 2007
- 年：2007
- 卷：129
- 期：15
- 页码：4551 - 4566
- 全文大小：516K
- 年卷期：v.129,no.15(April 18, 2007)
- ISSN：1520-5126
文摘
Acetylplatinum(II) complexes trans-[Pt(COMe)Cl(L)2] (L = PPh3, 2a; P(4-FC6H4)3, 2b) were foundto react with dialkyldisulfides R2S2 (R = Me, Et, Pr, Bu; Pr = n-propyl, Bu = n-butyl), yielding trinuclear 44cve (cluster valence electrons) platinum clusters [(PtL)3(
-SR)3]Cl (4). The analogous reaction of 2a-bwith Ph2S2 gave SPh bridged dinuclear complexes trans-[{PtCl(L)}2(-SPh)2] (5), whereas the addition ofBn2S2 (Bn = benzyl) to 2a ended up in the formation of [{Pt(PPh3)}3(3-S)(-SBn)3]Cl (6). Theoretical studiesbased on the AIM theory revealed that type 4 complexes must be regarded as triangular platinum clusterswith Pt-Pt bonds whereas complex 6 must be treated as a sulfur capped 48 ve (valence electrons) trinuclearplatinum(II) complex without Pt-Pt bonding interactions. Phosphine ligands with a lower donor capabilityin clusters 4 proved to be subject to substitution by stronger donating monodentate phosphine ligands (L'= PMePh2, PMe2Ph, PBu3) yielding clusters [(PtL')3(-SR)3]Cl (9). In case of the reaction of clusters 4 and9 with PPh2CH2PPh2 (dppm), a fragmentation reaction occurred, and the complexes [(PtL)2(-SMe)(-dppm)]Cl (12) and [Pt(-SMe)2(dppm)] (13) were isolated. Furthermore, oxidation reactions of cluster [{Pt(PPh3)}3(-SMe)3]Cl (4a) using halogens (Br2, I2) gave dimeric platinum(II) complexes cis-[{PtX(PPh3)}2(-SMe)2] (14, X = Br, I) whereas oxidation reactions using sulfur and selenium afforded chalcogen cappedtrinuclear 48 ve complexes [{Pt(PPh3)}3(3-E)(-SMe)3] (15, E = S, Se). All compounds were fullycharacterized 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 complex6, as well as for the dinuclear complexes trans-[{Pt(AsPh3)}2(-SPh)2] (5c), [{Pt(PPh3)}2(-SMe)(-dppm)]Cl (12a), and [{{PtBr(PPh3)}2(-SMe)2] (14a).
-SR)3]Cl (4). The analogous reaction of 2a-bwith Ph2S2 gave SPh bridged dinuclear complexes trans-[{PtCl(L)}2(-SPh)2] (5), whereas the addition ofBn2S2 (Bn = benzyl) to 2a ended up in the formation of [{Pt(PPh3)}3(3-S)(-SBn)3]Cl (6). Theoretical studiesbased on the AIM theory revealed that type 4 complexes must be regarded as triangular platinum clusterswith Pt-Pt bonds whereas complex 6 must be treated as a sulfur capped 48 ve (valence electrons) trinuclearplatinum(II) complex without Pt-Pt bonding interactions. Phosphine ligands with a lower donor capabilityin clusters 4 proved to be subject to substitution by stronger donating monodentate phosphine ligands (L'= PMePh2, PMe2Ph, PBu3) yielding clusters [(PtL')3(-SR)3]Cl (9). In case of the reaction of clusters 4 and9 with PPh2CH2PPh2 (dppm), a fragmentation reaction occurred, and the complexes [(PtL)2(-SMe)(-dppm)]Cl (12) and [Pt(-SMe)2(dppm)] (13) were isolated. Furthermore, oxidation reactions of cluster [{Pt(PPh3)}3(-SMe)3]Cl (4a) using halogens (Br2, I2) gave dimeric platinum(II) complexes cis-[{PtX(PPh3)}2(-SMe)2] (14, X = Br, I) whereas oxidation reactions using sulfur and selenium afforded chalcogen cappedtrinuclear 48 ve complexes [{Pt(PPh3)}3(3-E)(-SMe)3] (15, E = S, Se). All compounds were fullycharacterized 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 complex6, as well as for the dinuclear complexes trans-[{Pt(AsPh3)}2(-SPh)2] (5c), [{Pt(PPh3)}2(-SMe)(-dppm)]Cl (12a), and [{{PtBr(PPh3)}2(-SMe)2] (14a).