PREPARATION AND CRYSTAL-STRUCTURES OF SYN-[(MU-SPH)FE(CO)3]2, (C5H4SPH)2FE, (C5H5)FE(C5H4SPH), AND (C5H4SPH)FE(C5H4PPH2)

The reaction of (C5H4SPh)2Fe with Fe2(CO)9 in MeCN at 25-degrees-C under photolytic conditions has been found to afford a dimer, [(mu-SPh)Fe(CO)3]2, Whose X-ray structure exhibits a syn form. This reaction also yields (C5H5)Fe(C5H4SPh) as a byproduct, following the C-S bond cleavage. Stepwise functionalized of (C5H5)2Fe via selective transmetalation of (C5H4SnBu3)2Fe has led to the successful preparation of (C5H5)Fe(C5H4SPh) and (C5H4SPh)Fe(C5H4PPh2) in good yields. X-ray crystallographic studies of the title compounds have been carried out. (C5H4SPh)2Fe (2): monoclinic space group P2(1)/c, a = 6.099 (3) angstrom, b = 7.855 (1) angstrom, c = 19.027 (3) angstrom, beta = 99.12 (2)-degrees, V = 902.2 angstrom3, Z = 2, 1976 data with I0 > 2.5-sigma(I0) refined to R = 0.029 and R(w) = 0.035. (C5H5)Fe(C5H4SPh) (3): orthorhombic space group P2(1)2(1)2(1), a = 7.307 (8) angstrom, b = 9.018 (9) angstrom,c = 20.033 (3) angstrom, V = 1320.1 angstrom3, Z = 4, 1054 data with I0 > 2.5-sigma(I0) refined to R = 0.026 and R(w) = 0.028. (C5H4SPh)Fe(C5H4PPh2) (7): triclinic space group P1BAR, a = 9.675 (2) angstrom, b = 10.903 (3) angstrom, c = 12.899 (3) angstrom, alpha = 112.89 (3)-degrees, beta = 86.89 (2)-degrees, gamma = 113.53 (2)-degrees, V = 1141 angstrom3, Z = 2, 2567 data with I0 > 2.5-sigma(I0) refined to R = 0.032 and R(w) = 0.040. syn-[(mu-SPh)Fe(CO)3]2 (8): orthorhombic space group Pbca, a = 7.151 (2) angstrom, b = 20.847 (3) angstrom, c = 27.155 (4) angstrom, V = 4048.0 angstrom3, Z = 8,1247 data with I0 > 2.5-sigma(I0) refined to R = 0.043 and R(w) = 0.043.