Heterometallic derivatives of dicarbonylcyclopentadienylrhenium disulfide containing chromium pentacarbonyl and bis(triphenylphosphine)platinum

The reaction of Cp′Re(CO)2THF (Cp′ = C5H4Me), THF is tetrahydrofuran) with sulfur affords Cp′Re(CO)2S2(I) and [Cp′Re(CO)2]2S (II). The synthesized compounds are isolated chromatographically and characterized by X-ray diffraction analysis. The adduct Cp′Re(CO)2S2Cr(CO)5 (III) is synthesized by the reaction of compound I with Cr(CO)5(THF). The adduct CpRe(CO)2S2Cr(CO)5 (IV) is obtained similarly from known CpRe(CO)2S2 and Cr(CO)5(THF). The reaction of compound I with (PPh3)2Pt(C2Ph2) results in the removal of Ph2C2 and one sulfur atom to form Cp′Re(CO)2SPt(PPh3)2 (V). The structures of compounds I–V are determined by X-ray diffraction analysis (CIF files CCDC nos. 984554 (I), 984555 (II), 984556 (III), 984557 (IV), and 984558 (V)). Compound I contains the three-membered cycle ReS2 with the ordinary S-S bond (2.044(4) Å) and shortened Re-S bonds (average 2.434(3) Å). The three-membered cycle Re2S containing the ordinary Re-Re bond (2.932(1) Å) and shortened Re-S bonds (2.371(1) Å) is observed in compound II. In compounds III and IV, the formation of the ordinary S-Cr(CO)5 bond (2.406(1) Å) with one of the sulfur atoms almost does not change the geometry of the ReS2 fragment. The thermal decomposition of compound III proceeds with the elimination of six CO ligands in the range 110–160°C and then with the loss of CO and Cp′ in the range 160–430°C and the formation of the inorganic residue ReCrS2. Compound V contains the triangular framework ReSPt with the ordinary Pt-Re bond (2.7882(3) Å) and substantially shortened bonds Re-S (2.3984(9) Å) and Pt-S (2.2724(8) Å). It is assumed that compounds II and V can be presented as products of the π-coordination of the double bonds in Cp′(CO)2Re=S with the Cp′Re(CO)2 or Pt(PPh3)2 groups, respectively.