Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and...

Shinji Inomata; Keiichi Hitomi; Hiromi Tobita; Hiroshi Ogino

doi:10.1016/0020-1693(94)04051-6

Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′₂(Ph₂C₂S₂)₂Fe₄S₄](PF₆) and...

Shinji Inomata, Keiichi Hitomi, Hiromi Tobita, Hiroshi Ogino

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

Title full: Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′₂(Ph₂C₂S₂)₂Fe₄S₄](PF₆) and [Cp′₃(Ph₂C₂S₂)Fe₄S₅](PF₆)_n (n=1 and 2) (Cp′η₅-C₅Me₅). Structural change of the clusters accompanying electron transfer reactions. The cyclic voltammogram (CV) of the mixed-ligand cubane-type cluster Cp′₂(Ph₂C₂S₂)₂Fe₄S₄ (4) exhibits four reversible one-electron redox waves, corresponding to +2/+1, +1/0, 0/-1, and -1/-2 charged cluster couples. The CV of the mixed-ligand cubane-like cluster Cp′₃(Ph₂C₂S₂)Fe₄S₅ (5) exhibits four reversible one-electron redox waves, corresponding to +3/+2, + 2/+ 1, + 1/0, and 0/-1 charged cluster couples. Oxidized clusters, [4](PF₆)·CH₂Cl₂, [5](PF₆)·₂Me₂CO and [5](PF₆)₂·Me₂CO, were synthesized by chemical and/of electrochemical methods. The structures of these three salts were determined by X-ray crystallography and compared with those of the parent clusters 4 and 5. Both clusters 4 and 5 shrink as they are oxidized, indicating that the electrons are removed from antibonding orbitals. The crystallographic data are as follows: [4](PF₆)·CH₂Cl₂: orthorhombic, Pna2₁ with a = 17.259(3), b = 25.682(4), c = 12.628(2) Å, V= 5597(2) Å³, Z = 4 and R = 0.066; [5](PF₆)·2Me₂CO: triclinic, P1 with a = 14.112(4), b=17.712(3), c=13.325(4) Å, α= 108.08(2), β= 114.74(3), γ=84.00(1)^o, V=2874(1) Å³, Z=2 and R=0.066; [5](PF₆)₂·Me₂CO: triclinic, P1 with a=14.985(1), b=15.540(1), c=12.951(1) Å, α=93.40(2), β=95.04(1), γ=96.76(1)^o, V=2976(1) Å³, Z=2 and R=0.056.

Original language	English
Pages (from-to)	229-238
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	225
Issue number	1-2
DOIs	https://doi.org/10.1016/0020-1693(94)04051-6
Publication status	Published - 1994 Oct

Keywords

Cluster complexes
Crystal structures
Cyclopentadienyl complexes Mixed-ligand tetrairon-sulfur cluster
Electrochemistry
Electron transfer
Iron complexes
Sulfur complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{ecf7cb4f090b44969313fa1ce3fd106b,

title = "Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and...",

abstract = "Title full: Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and [Cp′3(Ph2C2S2)Fe4 S5](PF6)n (n=1 and 2) (Cp′η5-C5Me5). Structural change of the clusters accompanying electron transfer reactions. The cyclic voltammogram (CV) of the mixed-ligand cubane-type cluster Cp′2(Ph2C2S2)2 Fe4S4 (4) exhibits four reversible one-electron redox waves, corresponding to +2/+1, +1/0, 0/-1, and -1/-2 charged cluster couples. The CV of the mixed-ligand cubane-like cluster Cp′3(Ph2C2S2)Fe4 S5 (5) exhibits four reversible one-electron redox waves, corresponding to +3/+2, + 2/+ 1, + 1/0, and 0/-1 charged cluster couples. Oxidized clusters, [4](PF6)·CH2Cl2, [5](PF6)·2Me2CO and [5](PF6)2·Me2CO, were synthesized by chemical and/of electrochemical methods. The structures of these three salts were determined by X-ray crystallography and compared with those of the parent clusters 4 and 5. Both clusters 4 and 5 shrink as they are oxidized, indicating that the electrons are removed from antibonding orbitals. The crystallographic data are as follows: [4](PF6)·CH2Cl2: orthorhombic, Pna21 with a = 17.259(3), b = 25.682(4), c = 12.628(2) {\AA}, V= 5597(2) {\AA}3, Z = 4 and R = 0.066; [5](PF6)·2Me2CO: triclinic, P1 with a = 14.112(4), b=17.712(3), c=13.325(4) {\AA}, α= 108.08(2), β= 114.74(3), γ=84.00(1)o, V=2874(1) {\AA}3, Z=2 and R=0.066; [5](PF6)2·Me2CO: triclinic, P1 with a=14.985(1), b=15.540(1), c=12.951(1) {\AA}, α=93.40(2), β=95.04(1), γ=96.76(1)o, V=2976(1) {\AA}3, Z=2 and R=0.056.",

keywords = "Cluster complexes, Crystal structures, Cyclopentadienyl complexes Mixed-ligand tetrairon-sulfur cluster, Electrochemistry, Electron transfer, Iron complexes, Sulfur complexes",

author = "Shinji Inomata and Keiichi Hitomi and Hiromi Tobita and Hiroshi Ogino",

year = "1994",

month = oct,

doi = "10.1016/0020-1693(94)04051-6",

language = "English",

volume = "225",

pages = "229--238",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

number = "1-2",

}

TY - JOUR

T1 - Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and...

AU - Inomata, Shinji

AU - Hitomi, Keiichi

AU - Tobita, Hiromi

AU - Ogino, Hiroshi

PY - 1994/10

Y1 - 1994/10

N2 - Title full: Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and [Cp′3(Ph2C2S2)Fe4 S5](PF6)n (n=1 and 2) (Cp′η5-C5Me5). Structural change of the clusters accompanying electron transfer reactions. The cyclic voltammogram (CV) of the mixed-ligand cubane-type cluster Cp′2(Ph2C2S2)2 Fe4S4 (4) exhibits four reversible one-electron redox waves, corresponding to +2/+1, +1/0, 0/-1, and -1/-2 charged cluster couples. The CV of the mixed-ligand cubane-like cluster Cp′3(Ph2C2S2)Fe4 S5 (5) exhibits four reversible one-electron redox waves, corresponding to +3/+2, + 2/+ 1, + 1/0, and 0/-1 charged cluster couples. Oxidized clusters, [4](PF6)·CH2Cl2, [5](PF6)·2Me2CO and [5](PF6)2·Me2CO, were synthesized by chemical and/of electrochemical methods. The structures of these three salts were determined by X-ray crystallography and compared with those of the parent clusters 4 and 5. Both clusters 4 and 5 shrink as they are oxidized, indicating that the electrons are removed from antibonding orbitals. The crystallographic data are as follows: [4](PF6)·CH2Cl2: orthorhombic, Pna21 with a = 17.259(3), b = 25.682(4), c = 12.628(2) Å, V= 5597(2) Å3, Z = 4 and R = 0.066; [5](PF6)·2Me2CO: triclinic, P1 with a = 14.112(4), b=17.712(3), c=13.325(4) Å, α= 108.08(2), β= 114.74(3), γ=84.00(1)o, V=2874(1) Å3, Z=2 and R=0.066; [5](PF6)2·Me2CO: triclinic, P1 with a=14.985(1), b=15.540(1), c=12.951(1) Å, α=93.40(2), β=95.04(1), γ=96.76(1)o, V=2976(1) Å3, Z=2 and R=0.056.

AB - Title full: Syntheses and structures of mixed-ligand tetrairon-sulfur clusters, [Cp′2(Ph2C2S2) 2Fe4S4](PF6) and [Cp′3(Ph2C2S2)Fe4 S5](PF6)n (n=1 and 2) (Cp′η5-C5Me5). Structural change of the clusters accompanying electron transfer reactions. The cyclic voltammogram (CV) of the mixed-ligand cubane-type cluster Cp′2(Ph2C2S2)2 Fe4S4 (4) exhibits four reversible one-electron redox waves, corresponding to +2/+1, +1/0, 0/-1, and -1/-2 charged cluster couples. The CV of the mixed-ligand cubane-like cluster Cp′3(Ph2C2S2)Fe4 S5 (5) exhibits four reversible one-electron redox waves, corresponding to +3/+2, + 2/+ 1, + 1/0, and 0/-1 charged cluster couples. Oxidized clusters, [4](PF6)·CH2Cl2, [5](PF6)·2Me2CO and [5](PF6)2·Me2CO, were synthesized by chemical and/of electrochemical methods. The structures of these three salts were determined by X-ray crystallography and compared with those of the parent clusters 4 and 5. Both clusters 4 and 5 shrink as they are oxidized, indicating that the electrons are removed from antibonding orbitals. The crystallographic data are as follows: [4](PF6)·CH2Cl2: orthorhombic, Pna21 with a = 17.259(3), b = 25.682(4), c = 12.628(2) Å, V= 5597(2) Å3, Z = 4 and R = 0.066; [5](PF6)·2Me2CO: triclinic, P1 with a = 14.112(4), b=17.712(3), c=13.325(4) Å, α= 108.08(2), β= 114.74(3), γ=84.00(1)o, V=2874(1) Å3, Z=2 and R=0.066; [5](PF6)2·Me2CO: triclinic, P1 with a=14.985(1), b=15.540(1), c=12.951(1) Å, α=93.40(2), β=95.04(1), γ=96.76(1)o, V=2976(1) Å3, Z=2 and R=0.056.

KW - Cluster complexes

KW - Crystal structures

KW - Cyclopentadienyl complexes Mixed-ligand tetrairon-sulfur cluster

KW - Electrochemistry

KW - Electron transfer

KW - Iron complexes

KW - Sulfur complexes

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