249574-15-0Relevant academic research and scientific papers
Comparative reactivity study of cyclopentadienyl and fulvalene molybdenum complexes
Moreno, Consuelo,Arnanz, Avelina,Delgado, Salomé
, p. 139 - 150 (2008/10/08)
The reactions of cis-1,1′-[η5:η5- (C5H3CO2Me)2]Mo2 (CO)6 (1), in the presence of 1 equiv. of Me3NO, and [(η5-C5H4CO2/
Synthesis and characterization of FvW2(CO)4L2(SR)2 (L=CO, PPh2Me; R=H, i-Pr, CH2Ph, Ph) type (fulvalene)tungsten dihydrosulfides and dithiolates
Kovacs, Istvan,Shaver, Alan
, p. 31 - 40 (2007/10/03)
A direct, high-yield synthesis of (Et4N)2[FvW2(CO)6], where Fv=η5:η5-C10H8 (fulvalene), from W(CO)3(EtCN)3, Li2[C10H8], and Et4NBr is reported. It reacted with sulfur-transfer reagents, RSphthalimide (R=i-Pr, CH2Ph, Ph), to give the corresponding dithiolato complexes, FvW2(CO)6(SR)2. Treating the thiolato complexes, where R=i-Pr, CH2Ph, with CS2 gave thioxanthate derivatives FvW2(CO)4(S2CSR)2, via mixed RSW(CO)3(μ-Fv)(CO)2WS2CSR intermediates. The unstable bishydrosulfido complex FvW2(CO)6(SH)2 was obtained from FvW2(CO)6H2 and S8 via the mixed hydrido-hydrosulfido intermediate FvW2(CO)6(SH)H. FvW2(CO)6H2 also reacted with PPh2Me to give the ligand-substituted product FvW2(CO)4(PPh2Me)2H2, which provided access to the dianion Li2[FvW2(CO)4(PPh2Me)2] via methyllithium reduction. Similarly to its parent compound, [FvW2(CO)4(PPh2Me)2]2- also gave the corresponding dithiolato complexes, FvW2(CO)4(PPh2Me)2(SR)2 (R=i-Pr, CH2Ph, Ph), upon treatment with RSphthalimide. FvW2(CO)4(PPh2Me)2(SPh)2 was converted into FvW2(CO)4(PPh2Me)2(SH)2 under an atmosphere of H2S. All PPh2Me-substituted dithiolato complexes as well as the bishydrosulfide derivative exist in solution as an equilibrium mixture of D,L- and meso-cis,cis, cis,trans and trans,trans isomers. However, only the cis,cis isomer of the bishydrosulfido complex was present in the crystalline state.
