SYNTHETIC AND STRUCTURAL STUDIES ON SOME 1,3-DITHIA- AND 1,3-DISELENA-FERROCENOPHANES OF PHOSPHORUS AND ARSENIC. CRYSTAL AND MOLECULAR STRUCTURE OF 1,3-DITHIA-2-PHENYLARSINO-FERROCENOPHANE AT 163 K

Article abstract of DOI:10.1016/0022-328X(85)87279-X

A series of <3>ferrocenophanes of general formula Fe(C5H4E)2Y, (E = S, Se; Y = PC6H5, AsC6H5) has been prepared by the reaction of ferrocene-1,1'-dithiol or ferrocene-1,1'-diselenol with chloride complexes of the Group V elements.The phosphorus containing compounds react with elemental sulfur and with iodomethane to form a phosphine sulfide and a methiodide salt, respectively, whereas the arsenic containing compounds do not react under analogous conditions.Spectroscopic properties of the compounds are reported.The crystal structure of 1,3-dithia-2-phenylarsino-<3>ferrocenophane has been determined at 163 K.At that temperature the crystals have space group P2₁/c with a 20.286(5), b 5.730(2), c 15.526(4) Angstroem, β 125.90(3) deg and Z = 4.Least-squares refinement gave R = 0.062 for 2999 independent significant reflections whose intensities were measured by counter diffractometry.The As-S bond lengths are 2.252 and 2.255(1) Angstroem, and the S-As-S bond angle is 98.6(1) deg.The S atoms are displaced out of the ring planes away from the Fe atom by 0.06 and 0.07 Angstroem giving a non-bonded S...S separation of 3.42 Angstroem.The S-C bond lengths are 1.758 and 1.764(4) Angstroem, and the As-S-C bond angles are 97.3(2) and 99.3(1) deg.The cyclopentadienyl rings adopt an eclipsed conformation with a mean twist angle of 2.6 deg and the ring planes inclined at only 0.6 deg.The phenyl ring occupies the sterically less crowded exo-position with As-C 1.948(4) Angstroem, As-C-C angles of 116.6 and 123.6(3) deg, and S-As-C bond angles of 95.1 and 96.3(2) deg.