76452-71-6Relevant academic research and scientific papers
Oxidative coupling of mercaptide ligands in organometallic thiolate complexes
Treichel, Paul M.,Rosenhein, Laurence D.,Schmidt, Mark S.
, p. 3960 - 3965 (2008/10/08)
The one-electron oxidations of Fe(SPh)(CO)2(η-C5R5) by NOPF6 (R = Me, H) or AgPF6 (R = Me) produce diamagnetic complexes having the general formula [(η-C5R5)(CO)2Fe(μ-PhSSPh)Fe(CO) 2(η-C5R5)](PF6)2. The route to these complexes, which have bridging diphenyl disulfide ligands, probably involves loss of a nonbonding electron from the mercaptide ligand followed by coupling of the resulting ligand-centered radical species. The BF4- salt of the cyclopentadienyl complex may also be obtained by a reaction of [Fe(THF)(CO)2(η-C5H5)]BF4 and PhSSPh in a 2:1 ratio. Complexes with monodentate disulfide ligands, [Fe(RSSR)(CO)2(η-C5H5)]BF4 (R = Me, Ph), are obtained from 1:1 reactions of the disulfide and [Fe(THF)(CO)2(η-C5H5)]BF4. Oxidations of several monosubstituted Fe(SPh)(CO)(L)(η-C5R5) compounds (R = H, Me; L = PPhMe2, PPh2Me, PMe3, P(OPh)3, P(OEt)3) and two disubstituted compounds Fe(SPh)(CNR)2(η-C5H5) (R = m-C6H4OMe, m-C6H4CF3) produce dark solids having stoichiometries [Fe(SPh)(CO)(L)(η-C5H5)]PF6 and [Fe(SPh)(CNR)2(η-C5H5)]BF4. These compounds, as solids, have magnetic moments between 0.5 and 2.3 μB. Their behavior in solution is consistent with the existence of an equilibrium between paramagnetic and diamagnetic dimers. Oxidation of another disubstituted species, Fe(SPh)(P(OPh)3)2(η-C5H5), produces [Fe(SPh)(P(OPh)3)2(η-C5H 5)]PF6, a typical low-spin iron(III) complex; this is similar to results observed previously with disubstituted phosphine complexes, Fe(SPh)(L)2(η-C5H5) (L = PMe3, L2 = dppe).
NEW CYCLOPENTADIENYLIRON TRIMETHYLPHOSPHINE COMPLEXES
Treichel, P.M.,Komar, D.A.
, p. 77 - 88 (2007/10/02)
Preparations of X complexes (n = 1, 2, 3) are described.Irradiation of BF4 in acetonitrile gave BF4 which is a precursor to Fe(C5H5)(PMe3)2X (X = I, CN) and BF4.Reactions of Fe(C5H5)(CO)2X compounds (X = SPh, SiMe3, SnMe3, SnPh3) with PMe3 gave mono- and disubstituted products, Fe(C5H5)(CO)2-n(PMe3)nX.The reaction of Fe(C5H5)(CO)2Me with PMe3 gave Fe(C5H5)(CO)(PMe3)COMe or Fe(C5H5)(PMe3)2Me, depending on conditions.One electron oxidations of Fe(C5H5)(PMe3)2SPh, Fe(C5H5)(PMe3)2SnPh3 and PF6 produced 17 electron products which were isolable.
