THIOLATE DERIVATIVES OF BIS(DIPHENYLPHOSPHINOCYCLOPENTADIENYL)TITANIUM TI-PT AND TI-PD HETEROBIMETALLIC COMPOUNDS

Reactions of [{eta(5)-C5H4P(C6H5)(2)}2TiCl2] with HSR in the presence of Et(3)N gave the new compounds [{eta(5)-C5H4P(C6H5)(2)}Ti-2(SR)(2)] (R = CH2C6H5 (1), C6H5, (2), CH2CH3 (3), C6F5 (4) and [{eta(5)-C5H4P(C6H5)(2)}2TiCl(SC6H11)] (5). The complex [{eta(5)-C5H4P(C6H5)(2)}Ti-2(SC6F5)(2)] can be prepared in higher yield by reaction of TlSC6F5 with [{eta(5)-C5H4P(C6H5)(2)}2TiCl2] in toluene. These compounds are of interest as metalloligands to form bimetallic and trimetallic species. The treatment of [{eta(5)-C5H4P(C6H5)(2)}2TiCl2] or [{eta(5)-C5H4P(C6H5)(2)}Ti-2(SC6H5)(2)] with cis-[M(C6F5)(2)(THF)(2)] gave the new heterobimetallic complexes [Cl2Ti{mu-C5H4P(C6H5)(2)}(2)M(C6F5)(2)] [M = Pt (6) or Pd (7)] and [(C6H5S)(2)Ti{mu-C5H4P(C6H5)(2)}Pt-2(C6F5)(2)] (8). In all cases the THF of the cis-[M(C6F5)(2)(THF)(2)] was easily replaced by the phosphine rather than chloride or thiolate. The compounds have been characterized by H-1, P-31 and F-19 NMR spectroscopies and FAB mass spectrometry.