The first multiply chalcogen-bridged metallocene compound 1,1',2,2'-bis(1,2,3-trithia-[3])ferrocenophane 1, a species featuring two S3 linkages around the metallocene nucleus, has been prepared by the lithiation of ferrocene 1,1'-dithiol, followed by treatment with elemental sulfur. The sulfur linkages lie in adjacent positions on the cyclopentadienyl rings and, in solution, the compound exists as a mixture of two diastereomers due to the orientation of the trisulfur bridges. Proton NMR spectra at ambient temperatures indicate the predominance of the chair-chair isomer 1a (70%) over the less-favoured chair-boat species 1b (30%). The structure of 1 has been determined by X-ray diffraction and the crystals are monoclinic, space group P2(1)/n with a = 6.830(1), b = 13.310(1), c = 13.929(1) angstrom, beta = 99.70(1)-degrees and Z = 4. Least-squares refinement give R = 0.030 for 1650 observed reflections whose intensities were measured on an area detector diffractometer with Mo-Kalpha radiation. The S-S bond lengths are 2.054(4), 2.065(4), 2.044(4) and 2.054(4) angstrom and the S(1)-S(2)-S(3) and S(4)-S(5)-S(6) bond angles are 105.1(2) and 103.5(2)-degrees respectively. The S-C bond lengths are 1.752(6), 1.760(6), 1.752(6) and 1.755(6) angstrom with S-S-C bond angles of 102.3(2), 102.2(2), 102.4(3) and 101.8(2)-degrees. The cyclopentadienyl rings are in an eclipsed conformation and are mutually parallel. The trisulfide linkages are in a chair-chair conformation with non-bonding separation of 3.25 and 3.23 angstrom for S(1) ... S(3) and S(4) ... S(6) respectively.
