Trinuclear Fe―M―S complexes containing a linear Fe―M―Fe array and a bridging S2MS2 unit. Electronic structures and crystal and molecular structures of the [(C6H5)4P]2[Cl2FeS2MS2FeCl2] (M=Mo, W) complexes
Inorganic chemistry, Vol.23(6), pp.741-749
1984
: 10.1021/ic00174a021
The title complexes [Cl2FeS2MS2FeCl2]2- (M = M0 (I), W (II)) are obtained either by oxidation of the [(PhS)2FeS2MS2]2- complexes with FeCl3.6H2O or by direct syntheses from FeCl2 and the MS42- anions in acetonitrile solution. Complexes I and II undergo dissociation in donor solvents with loss of FeCl2 and formation of the dinuclear [Cl2FeS2MoS2]2- complexes. The (C6H5)4P+ salt of the [Cl2FeS2MoS2FeCl2]2- anion (I) crystallizes in the triclinic space group Pi with two molecules per unit cell. The cell dimensions for I are a = 10.197 (2) Å, b = 13.054 (2) Å, c = 20.164 (3) Å, a = 100.46 (2)°, β = 100.61 (1)°, and = 100.92 (1)°. The tungsten complex [(C6H5)4P]2[Cl2FeS2WS2FeCl2] (II) is X-ray isomorphous and isostructural. The cell dimensions for II are a = 10.215 (6) A, b = 13.071 (5) Å, c = 20.187 (7) Å, a = 100.54 (3)°, β = 100.58 (2)°, and 7 = 100.97 (2)°. Intensity data for I and II were collected with a four-circle computer-controlled diffractometer with use of the-2 scan technique. In all structures, all non-hydrogen atoms were refined with anisotropic temperature factors and the hydrogen atoms were included in the structure factor calculations but not refined. Refinement by full-matrix least squares of 550 parameters on 5125 data for I and 550 parameters on 9711 data for II gave final R values of 0.058 and 0.050, respectively. The structures of these trinuclear complexes consist of a tetrahedral MS42- unit bridging two FeCl2 groups. The Fe-Mo distances in I at 2.771 (2) and 2.781 (2) Å and the Fe-Fe distance at 5.552 (2) Å are all shorter than the corresponding distances in II, which are 2.795 (1), 2.808 (1), and 5.603 (1) Å, respectively. The Fe-M-Fe angles in I and II are 179.37 (6) and 179.25 (4)°, respectively. Average values of other structural parameters are as follows: for I, Fe-S = 2.296 (4) A, FeCl = 2.234 (1) X, Mo-S = 2.206 (2) A, Fe-Sb-Mo = 76.1 (1)°; for II, Fe-S = 2.320 (6) A, FeCl = 2.233 (10) A, W-S = 2.209 (5) A, Fe-St,-W = 76.4 (2)°. The structural as well as Mossbauer and magnetic properties of I and II indicate that the WS42- unit is a weaker bridging ligand than MoS42-. Chemical and electrochemical studies show that I and II undergo a one-electron reduction followed by loss of Cl- and formation of the ([Fe2Cl3S2MS2]2-)x anions.
- Trinuclear Fe―M―S complexes containing a linear Fe―M―Fe array and a bridging S2MS2 unit. Electronic structures and crystal and molecular structures of the [(C6H5)4P]2[Cl2FeS2MS2FeCl2] (M=Mo, W) complexes
- D Coucouvanis - Univ. Iowa, dep. chemistryE. D Simhon - Univ. Iowa, dep. chemistryP Stremple - Univ. Iowa, dep. chemistryM Ryan - Univ. Iowa, dep. chemistryD Swenson - Univ. Iowa, dep. chemistryN. C Baenziger - Univ. Iowa, dep. chemistryA Simopoulos - Univ. Iowa, dep. chemistryV Papaefthymiou - Univ. Iowa, dep. chemistryA Kostikas - Univ. Iowa, dep. chemistryV Petrouleas - Univ. Iowa, dep. chemistry
- Journal article
- Inorganic chemistry, Vol.23(6), pp.741-749
- American Chemical Society
- 10.1021/ic00174a021
- 0020-1669
- 1520-510X
- English
- 1984
- Chemistry
- 9984622750002771
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