85629-29-4Relevant academic research and scientific papers
Reactions of the thiocarbene complex Cp(CO)2Fe[CH(SMe)]+ with nucleophiles
Yu, Yeung S.,Angelici, Robert J.
, p. 1018 - 1026 (2008/10/08)
The thiocarbene complexes Cp(CO)(L)Fe[CH(SMe)]+, where L = CO, PPh3, or P(OPh)3, are prepared by H- addition to Cp(CO)(L)Fe[C(SMe)2]+ to give Cp(CO)(L)Fe[CH(SMe)2], which upon treatment with CF3SO3H, HBF4, or (Ph3C)PF6 provides Cp(CO)(L)Fe[CH(SMe)]+. Reactions of the electrophilic Cp-(CO)2Fe[CH(SMe)]+ with a range of phosphines and phosphites, L (PPh2Me, PPh3, PPh2Cl, PCl3, P(OPh)3, P(OCH2)3CMe, PPh2H, P-c-Hx2H, PPhH2, P-c-HxH2), give the carbene adducts (or ylides) Cp(CO)2Fe[CH(SMe)(L)]+, most of which are air-stable, while the PCl3 adduct is too unstable to isolate. An X-ray structural determination of Cp(CO)2Fe[CH(SMe)(P(OCH2)3CMe)]PF6 (monoclinic, P21/c, a = 10.359 (3) ?, b = 12.284 (4) ?, c = 16.234 (4) ?, β = 95.25 (3)°, V = 2057 ?3, Z = 4) confirms that the P atom is bonded to the carbene carbon in this and the other adducts. When Cp(CO)2Fe[CH(SMe)(PPh3)+ is heated at 200°C, Cp(CO)2Fe(PPh3)+ (88% yield) and cis- and trans-(MeS)CH=CH(SMe) are formed among other products. When Cp(CO)2Fe[CH(SMe)(PR2H)]+, where R = Ph or c-Hx, is pyrolyzed, rearrangement to the phosphine complex Cp(CO)2Fe[PR2(CH2SMe)]+ (20% yield) occurs. The phosphonium proton in Cp(CO)2Fe[CHSMe)(PPh2)H)]+ is removed by n-BuLi or Et3N to give Cp(CO)2Fe[CH(SMe)(PPh2)], which upon alkylation with MeOSO2F yields Cp(CO)2Fe[CH(SMe)(PPh2Me)]+. The carbene ligand in Cp-(CO)2Fe[CH(SMe)]+ reacts rapidly with water to give equal amounts of Cp(CO)2Fe(CH2SMe) and CpFe(CO)3+ together with MeSH; deuterium-labeling experimental results are consistent with a mechanism involving a formyl Cp(CO)2Fe[C(=O)H] intermediate. Diazomethane (CH2N2) reacts with Cp(CO)2Fe[CH(SMe)]+ to yield the complex Cp(CO)2Fe[SMe(CH=CH2)]+ in which the olefin is coordinated to the metal through the S atom.
