THIOLATE, THIOETHER, AND THIOL DERIVATIVES OF IRON(0) CARBONYLS Academic Article uri icon

abstract

  • A new series of anionic complexes of iron tetracarbonyl monofunctionalized with the ligand [RS 1, [RSFe(CO)4 ] (R = Ph, Et, Me, H), have been synthesized and characterized. The compound [PPN] [PhSFe(CO)4] was formed in the reaction of [PPN] [HFe(CO)4] and PhSSPh. The [PhSFe(CO)4] anion was characterized by X-ray diffraction as its [PPN+] salt and found to be a typical trigonal-bipyramidal complex in which the phenylthiolate ligand occupies an axial position with a Fe-S bond distance of 2.332 (5) and Fe-S-C(Ph) - 111.3 (6). The salt crystallized in the orthorhombic space group Pbc21, with a = 9.529 (4) , b = 21.493 (9) , c - 20.185 (9) , V = 4134 (3) 3, and Z = 2. Other members of the series of complexes, [RSFe(CO)4 ], were best obtained by ligand exchange of [RS] and the labile thioether complex (PhSMe)Fe(CO)4. The latter was produced from the low-temperature alkylation of the [PhSFe(CO)4 ]. Protonation of the thiolates (R = Ph, Et, Me, H) ultimately leads to formation of H2 and Fe2(-SR)2(CO)6; however, the intermediate thiol, (RSH)Fe(CO)4, could be observed at -78 to -40 C for R = Et, Me. The PhSH and HSH derivatives were unstable even at -78 C. 1989, American Chemical Society. All rights reserved.

published proceedings

  • JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

author list (cited authors)

  • LIAW, W. F., KIM, C., DARENSBOURG, M. Y., & RHEINGOLD, A. L.

citation count

  • 44

complete list of authors

  • LIAW, WF||KIM, C||DARENSBOURG, MY||RHEINGOLD, AL

publication date

  • May 1989