Abstract
Full title: Addition of activated acetylenes to coordinated polysulfide ligands. 2. Synthesis of the Fe2[S2C2(COOCH3)2] 42- dithiolene complex by the addition of CH3OOCC≡CCOOCH3 to the (Fe2S12)2- anion. Crystal and molecular structure of (Ph4P)2Fe2[S2C 2(COOCH3)2]4. The reaction of (Ph4P)2Fe2S12 and CH3OOCC≡CCOOCH3 in dimethylformamide (DMF) in a 1:2 molar ratio proceeds readily to afford the new (Ph4P)2Fe2[S2C 2(COOCH3)2]4·2DMF complex in 69% yield. The complex crystallizes in the triclinic space group P1 (Z = 2) with one molecule per unit cell. The cell dimensions are a = 12.343 (4) Å, b = 13.710 (5) Å, c = 14.787 (8) Å, a = 63.79 (4)°, β = 68.23 (4)°, and γ = 85.32 (3)°. Intensity data were collected with a P3F Nicolet automated diffractometer using the θ-2θ scan mode. All the non-hydrogen atoms were refined anisotropically. Full-matrix least-squares refinement of 351 parameters on 2886 data gave final Rw = 7.03% and R = 5.15%. The hydrogen atoms were incuded in their calculated positions but were not refined. The anion is located on the crystallographic center of symmetry with the [Fe(S2C2(COOCH3)2)2] - fragment as the asymmetric unit. The Fe(III) atoms are found in a tetragonal-pyramidal coordination environment with one basal sulfur S(3) on one Fe atom serving as the axial ligand for the other centrosymmetrically related Fe atom. The Fe-S(1) and Fe-S(2) basal bond lengths of the terminal ligand are 2.230 (2) Å. The other two basal Fe-S(3) and Fe-S(4) bonds of the bridging ligand are 2.256 (2) and 2.243 (2) Å, respectively. The axial bridging Fe-S(3)′ bond length is 2.466 (2) Å. Solution electronic spectral, electrochemical, 1H NMR spectroscopic, and magnetic studies show that the dimeric structure is preserved in weakly dielectric media while in highly polar coordinating media the axial bridging interactions within the dimer are replaced by solvent coordination and the monomeric structure prevails with the system in a paramagnetic S = 3/2 state. The magnetic moments range from 3.78 to 1.87 μB in different solutions in the order Me2SO ∼ DMF > CH3CN > CH2Cl2. EPR spectra at 93 K in DMF and Me2SO show absorptions characteristic of a S = 3/2 spin ground state.
| Original language | English |
|---|---|
| Pages (from-to) | 403-409 |
| Number of pages | 7 |
| Journal | Inorganic Chemistry |
| Volume | 23 |
| Issue number | 4 |
| Publication status | Published - 1984 |
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Addition of activated acetylenes to coordinated polysulfide ligands. 2. Synthesis of the Fe2[S2C2(COOCH3)2] 42- dithiolene complex by the addition of CH3OOCC≡CCOOCH3 to the (Fe2S12)2- anion. Crystal and molecular ... / Kanatzidis, Mercouri G; Coucouvanis, D.
In: Inorganic Chemistry, Vol. 23, No. 4, 1984, p. 403-409.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Addition of activated acetylenes to coordinated polysulfide ligands. 2. Synthesis of the Fe2[S2C2(COOCH3)2] 42- dithiolene complex by the addition of CH3OOCC≡CCOOCH3 to the (Fe2S12)2- anion. Crystal and molecular ...
AU - Kanatzidis, Mercouri G
AU - Coucouvanis, D.
PY - 1984
Y1 - 1984
N2 - Full title: Addition of activated acetylenes to coordinated polysulfide ligands. 2. Synthesis of the Fe2[S2C2(COOCH3)2] 42- dithiolene complex by the addition of CH3OOCC≡CCOOCH3 to the (Fe2S12)2- anion. Crystal and molecular structure of (Ph4P)2Fe2[S2C 2(COOCH3)2]4. The reaction of (Ph4P)2Fe2S12 and CH3OOCC≡CCOOCH3 in dimethylformamide (DMF) in a 1:2 molar ratio proceeds readily to afford the new (Ph4P)2Fe2[S2C 2(COOCH3)2]4·2DMF complex in 69% yield. The complex crystallizes in the triclinic space group P1 (Z = 2) with one molecule per unit cell. The cell dimensions are a = 12.343 (4) Å, b = 13.710 (5) Å, c = 14.787 (8) Å, a = 63.79 (4)°, β = 68.23 (4)°, and γ = 85.32 (3)°. Intensity data were collected with a P3F Nicolet automated diffractometer using the θ-2θ scan mode. All the non-hydrogen atoms were refined anisotropically. Full-matrix least-squares refinement of 351 parameters on 2886 data gave final Rw = 7.03% and R = 5.15%. The hydrogen atoms were incuded in their calculated positions but were not refined. The anion is located on the crystallographic center of symmetry with the [Fe(S2C2(COOCH3)2)2] - fragment as the asymmetric unit. The Fe(III) atoms are found in a tetragonal-pyramidal coordination environment with one basal sulfur S(3) on one Fe atom serving as the axial ligand for the other centrosymmetrically related Fe atom. The Fe-S(1) and Fe-S(2) basal bond lengths of the terminal ligand are 2.230 (2) Å. The other two basal Fe-S(3) and Fe-S(4) bonds of the bridging ligand are 2.256 (2) and 2.243 (2) Å, respectively. The axial bridging Fe-S(3)′ bond length is 2.466 (2) Å. Solution electronic spectral, electrochemical, 1H NMR spectroscopic, and magnetic studies show that the dimeric structure is preserved in weakly dielectric media while in highly polar coordinating media the axial bridging interactions within the dimer are replaced by solvent coordination and the monomeric structure prevails with the system in a paramagnetic S = 3/2 state. The magnetic moments range from 3.78 to 1.87 μB in different solutions in the order Me2SO ∼ DMF > CH3CN > CH2Cl2. EPR spectra at 93 K in DMF and Me2SO show absorptions characteristic of a S = 3/2 spin ground state.
AB - Full title: Addition of activated acetylenes to coordinated polysulfide ligands. 2. Synthesis of the Fe2[S2C2(COOCH3)2] 42- dithiolene complex by the addition of CH3OOCC≡CCOOCH3 to the (Fe2S12)2- anion. Crystal and molecular structure of (Ph4P)2Fe2[S2C 2(COOCH3)2]4. The reaction of (Ph4P)2Fe2S12 and CH3OOCC≡CCOOCH3 in dimethylformamide (DMF) in a 1:2 molar ratio proceeds readily to afford the new (Ph4P)2Fe2[S2C 2(COOCH3)2]4·2DMF complex in 69% yield. The complex crystallizes in the triclinic space group P1 (Z = 2) with one molecule per unit cell. The cell dimensions are a = 12.343 (4) Å, b = 13.710 (5) Å, c = 14.787 (8) Å, a = 63.79 (4)°, β = 68.23 (4)°, and γ = 85.32 (3)°. Intensity data were collected with a P3F Nicolet automated diffractometer using the θ-2θ scan mode. All the non-hydrogen atoms were refined anisotropically. Full-matrix least-squares refinement of 351 parameters on 2886 data gave final Rw = 7.03% and R = 5.15%. The hydrogen atoms were incuded in their calculated positions but were not refined. The anion is located on the crystallographic center of symmetry with the [Fe(S2C2(COOCH3)2)2] - fragment as the asymmetric unit. The Fe(III) atoms are found in a tetragonal-pyramidal coordination environment with one basal sulfur S(3) on one Fe atom serving as the axial ligand for the other centrosymmetrically related Fe atom. The Fe-S(1) and Fe-S(2) basal bond lengths of the terminal ligand are 2.230 (2) Å. The other two basal Fe-S(3) and Fe-S(4) bonds of the bridging ligand are 2.256 (2) and 2.243 (2) Å, respectively. The axial bridging Fe-S(3)′ bond length is 2.466 (2) Å. Solution electronic spectral, electrochemical, 1H NMR spectroscopic, and magnetic studies show that the dimeric structure is preserved in weakly dielectric media while in highly polar coordinating media the axial bridging interactions within the dimer are replaced by solvent coordination and the monomeric structure prevails with the system in a paramagnetic S = 3/2 state. The magnetic moments range from 3.78 to 1.87 μB in different solutions in the order Me2SO ∼ DMF > CH3CN > CH2Cl2. EPR spectra at 93 K in DMF and Me2SO show absorptions characteristic of a S = 3/2 spin ground state.
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M3 - Article
VL - 23
SP - 403
EP - 409
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 4
ER -