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 ...

Mercouri G Kanatzidis, D. Coucouvanis

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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 languageEnglish
Pages (from-to)403-409
Number of pages7
JournalInorganic Chemistry
Volume23
Issue number4
Publication statusPublished - 1984

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polysulfides
Alkynes
acetylene
Anions
Dimethylformamide
anions
Ligands
Atoms
Crystals
ligands
synthesis
crystals
atoms
Bond length
cells
diffractometers
Diffractometers
hydrogen atoms
Magnetic moments
molecular structure

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{f0e80e77d53c4f35a61392ec236b8af4,
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 ...",
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) {\AA}, b = 13.710 (5) {\AA}, c = 14.787 (8) {\AA}, 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) {\AA}. The other two basal Fe-S(3) and Fe-S(4) bonds of the bridging ligand are 2.256 (2) and 2.243 (2) {\AA}, respectively. The axial bridging Fe-S(3)′ bond length is 2.466 (2) {\AA}. 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.",
author = "Kanatzidis, {Mercouri G} and D. Coucouvanis",
year = "1984",
language = "English",
volume = "23",
pages = "403--409",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

}

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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