New (1‐Phosphanylferrocen‐1′‐ and ‐2‐yl)methyl‐Linked Diaminocarbene Ligands: Synthesis and Rhodium(I) Complexes

Two ferrocenylmethanols, [1′‐(diphenylthiophosphanyl)ferrocen‐1‐yl]methanol ( 3 ) and [2‐(diphenylthiophosphanyl)ferrocen‐1‐yl]methanol ( 6 ), have been converted in one step into the 1,1′‐ and 1,2‐ferrocenediyl‐linked thiophosphane/ N ‐R‐imidazolium salts 4a , b and 7a , b ( a : R = Me; b : R = 2,4,6‐Me 3 C 6 H 2 or Mes). This straightforward method allows the linkage of an imidazolium group to a ferrocene unit with a nonsubstituted methylene bridge. After desulfurisation of the phosphane group, the ligands reacted with an Rh I precursor, in the presence of t BuOK, to give cationic complexes 9a , b and 10a , b . All compounds were characterised by elemental analysis, NMR spectroscopy and mass spectrometry. The molecular structures of compounds 4a , 7a and 9a were determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)