90432-13-6Relevant articles and documents
Thiophosphoryl complexes of bis(cyclopentadienyl)titanium. 1. Syntheses, interconversions, and structures
Zank, Gregg A.,Rauchfuss, Thomas B.
, p. 1191 - 1199 (2008/10/08)
The reaction of (MeCp)2Ti(CO)2 (MeCp = η5-CH3C5H4) with perthiophosphinic acid anhydrides, R2P2S4, gives compounds of the formula (MeCp)2TiS4P2R2 (R = 4-C6H4OCH3 (An), 2a; R = 4-C6H4OC2H5 (Pn), 2c) or (MeCp)2TiS3PR (R = t-Bu, 3b; R = 3-cyclohexenyl, 3c). The TiS4P2R2 compounds could also be prepared from LiBHEt3-reduced R2P2S4 and (MeCp)2TiCl2 (or Cp2TiCl2). Spectroscopic studies indicate that the type 2 compounds contain TiSPPS rings. The reaction of Li2S with R2P2S4 gives Li2S3PR that was isolated in the case where R = An, 4. S3PR2- reacted with (MeCp)2TiCl2 to give the aforementioned (MeCp)2TiS3PR compounds in addition to 3a where R = An. 31P NMR studies suggest that 2a and 3a are in facile equilibrium (Keq = 0.22), consistent with this 3a was found to react with [PhPS]3 yielding a 1:2:1 mixture of the Ph2, AnPh, and An2 derivatives of the TiS4P2 compounds. Compound 3a reacts with NiCl2(Ph2PC2H4PPh2) faster than does 2a giving (MeCp)2TiCl2 and Ni(S3PAn)(Ph2PC2H4PPh2). A single-crystal X-ray diffraction study confirmed that 3a contains a TiSPS ring. 3a crystallizes in the space group P21/c with a = 7.304 (2) A?, b = 13.716 (3) A?, c = 23.995 (6) A?, and β = 111.28 (2)°. The structural parameters of 3a are compared with (Me5C5)2TiS3 and Me2P2S4.
