Re2(CO)6(μ-thpymS)2 (thpymSH = pyrimidine-2-thiol) as a versatile precursor to mono- and polynuclear complexes: X-ray crystal structures of fac-Re(CO)3(PPh3)(κ2-thpymS) and two isomers of ReRu3(CO)13(μ3-thpymS)

The dirhenium complexes Re2(CO)6(μ-thpymS)2 (1) and eq-Re2(CO)9{κ1-(S)-SN2C4H8} (2) are obtained from the reaction of tetrahydropyrimidine-2-thiol (thpymSH) with Re2(CO)8(NCMe)2 or Re2(CO)10. Complex 1 proves to be an excellent precursor to a range of monometallic and cluster complexes acting as a source of “Re(CO)3(thpymS)”. Thus, reactions with triphenylphosphine (PPh3) and bis(diphenylphosphino)methane (dppm) afford mononuclear fac-Re(CO)3(PPh3)(κ2-thpymS) (3) and fac-Re(CO)3(κ1-dppm)(κ2-thpymS) (4), respectively. A crystal structure of 3 reveals that the pyrimidine-2-thiolate binds in a chelating fashion. Reactions with M3(CO)12 (M = Ru, Os) at moderate temperatures afford mixed-metal clusters. With Ru3(CO)12 in boiling thf isomeric tetranuclear butterfly clusters ReRu3(CO)13(μ3-thpymS) (5–6) result which differ in the position of the capping pyrimidine-2-thiolate ligand on the cluster surface. Thus in the kinetic isomer 5, the pyrimidine-2-thiolate caps the ReRu2 face while in the thermodynamic isomer 6 it caps the Ru3 face. A similar reaction with Os3(CO)10(NCMe)2 in boiling benzene affords predominantly the ReOs2-capped tetranuclear cluster ReOs3(CO)13(μ3-thpymS) (7), together with small amounts of (μ-H)Os3(CO)9(μ3-thpymS) (8) resulting from loss of rhenium. Cluster 7 is stable in refluxing toluene but slowly converts to isomeric 9 in xylene at 140 °C but only in low yields. The crystal structures of isomeric 5–6 have been solved and show only small variations in the cluster core geometry. Density functional calculations show that clusters 6 and 9 are slightly more stable than 5 (ΔG 2.0 kcal mol−1) and 7 (ΔG 1.5 kcal mol−1), respectively, and a mechanism is proposed for these conversions in which the pyrimidine-2-thiolate becomes bidentate after release of the pyrimidine group.

Graphical abstractReactivity of the dirhenium complex Re2(CO)6(μ-thpymS)2 with phosphines and trimetallic carbonyls has been investigated.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Reactions of tetrahydropyrimidine-2-thiol (thpymSH) with Re2(CO)8L2 (L = CO, MeCN). ► Synthesis and characterization of dirhenium complexes. ► Reactions of Re2(CO)6(μ-thpymS)2 with M3(CO)10L2 (M = Ru, Os; L = CO, MeCN). ► Synthesis and characterization of tetranuclear mixed-metal complexes. ► Thermally induced cluster isomerization.