Reactivity of [CpCr(CO)3]2 towards thione (CS) moieties in some sulfur-containing substrates

The reaction of [CpCr(CO)₃]₂ (Cp = η⁵-C₅H₅) (1) with 1 mol equivalent of 2,5-dimercapto-1,3,4-thiadiazole (DMcTH₂) at ambient temperature led to the isolation of a reddish-brown crystalline solid of CpCr(CO)₃(η¹-DMcTH) (5) and a green solid of CpCr(CO)₃H (2) in yields of ca. 28% and 30%, respectively, along with some [CpCr(CO)₂]₂ (3) and [CpCr(CO)₂]₂S (4). The reaction of 1 with 1 mol equivalent of vinylene trithiocarbonate (SCS(CH)₂S) (VTTC) at 90 °C led to the isolation of a red crystalline solid of CpCr(CO)₂(η²-SCHSC₂H₂) (6) in ca. 15% yield while the reaction of 1 with isopropylxanthic disulfide ((CH₃)₂CHOCS₂)₂ resulted in the formation of CpCr(CO)₂(η²-S₂COCH(CH₃)₂) (8) in ca. 80% yield. The complexes 5, 6 and 8 have been determined by single crystal X-ray diffraction analysis.     

Tetracarbonyliron adducts of Cp2Cr2(CO)4(μ-η2-P2). Syntheses and crystal structures of Cp2Cr2(CO)4P2[Fe(CO)4] m (m=1 and 2)

Cp₂Cr₂(CO)₄( - ² - P₂), 1, reacts with one molar equivalent of Fe₂(CO)₉ in THF to yield the mono- and di-iron complexes, Cp₂Cr₂(CO)₄P₂[Fe(CO)₄], 2, (16.5% yield) and Cp₂Cr₂(CO)₄P₂[Fe(CO)₄]₂, 3, (16.9% yield), as dark magenta brown and dark greenish brown crystals, respectively. Both complexes were characterized by single-crystal X-ray diffraction analysis. Crystal data –2: space group =P2₁/c,a=17.024(1) Å,b=8.180(1) Å,c=30.891(2) Å, =100.953(5)°,V=4223.4(7)ų,Z=8, 3743 observed reflections,R _F=0.033; 3: space group P1,a=10.209(2) Å,b=10.212(2) Å,c=15.989(3) Å, =106.93(1)°, =91.87(1)°, =119.50(1)°,V=1356.5(4) ų,Z=2, 3489 observed reflections,R _F=0.029.     

Synthetic, X-ray structural and protonation studies of CpCr(CO)2SPy and CpCr(CO)2SPym (SPy = C5H4NS, SPym = C4H3N2S)

The facile reaction of [CpCr(CO)₃]₂ (Cp = η⁵-C₅H₅) (1) with one mole equivalent of 2,2′-dithiodipyridine ((C₅H₄NS)₂(SPy)₂) at ambient temperature led to the isolation of dark brown crystalline solids of CpCr(CO)₂(η²-SPy) (2) in ca. 72% yield. 2 undergoes quantitative conversion to CpCrCl₂(η¹-SPyH) (3) with HCl. The reaction 1 with one mole equivalent of 2-mercaptopyrimidine (C₄H₃N₂SHHSPym) at ambient temperature led to the isolation of reddish-brown crystalline solids of CpCr(CO)₂(η²-SPym) (4) and green solids of CpCr(CO)₃H (5) in yields of ca. 42% and 46%, respectively. Reaction of 4 with HCl and subsequent workup in acetonitrile resulted in the cleavage of the thiolate ligand, giving the 15-electron chromium(III) species CpCrCl₂(CH₃CN) (6) and free 2-mercaptopyrimidine. The complexes 2-4 have been determined by single X-ray diffraction analysis.