Two new terpyridine dimanganese complexes: A manganese(III,III) complex with a single unsupported oxo bridge and a manganese(III,IV) complex with a dioxo bridge. Synthesis, structure, and redox properties

Carole Baffert, Marie Noëlle Collomb, Alain Deronzier, Jacques Pécaut, Julian Limburg, Robert H. Crabtree, Gary W Brudvig

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Abstract

Two new terpyridine dimanganese oxo complexes [Mn2III,IV(μ-O)2(terpy)2(CF 3CO2)2]+ (3) and [Mn2III,III(μ-O)(terpy)2-(CF 3CO2)4] (4) (terpy = 2,2′:6,2″-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn2III,IV(μ-O)2(terpy)2(H 2O)2]3+ (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF3CO2- ligands on each manganese adopt a cis geometry to each other; one CF3CO2- is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF3CO2- have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH3CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH3CN solution into the mixed-valent complex 3 and the mononuclear complex [MnIIterpy)2]2+ (2), thereby preventing the observation of its electrochemical behavior.

Original languageEnglish
Pages (from-to)1404-1411
Number of pages8
JournalInorganic Chemistry
Volume41
Issue number6
DOIs
Publication statusPublished - Mar 25 2002

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Manganese
manganese
synthesis
Geometry
geometry
Oxygen
Ligands
solid state
X rays
Atoms
ligands
Oxidation-Reduction
oxygen
configurations
atoms
x rays

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  • Inorganic Chemistry

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Two new terpyridine dimanganese complexes : A manganese(III,III) complex with a single unsupported oxo bridge and a manganese(III,IV) complex with a dioxo bridge. Synthesis, structure, and redox properties. / Baffert, Carole; Collomb, Marie Noëlle; Deronzier, Alain; Pécaut, Jacques; Limburg, Julian; Crabtree, Robert H.; Brudvig, Gary W.

In: Inorganic Chemistry, Vol. 41, No. 6, 25.03.2002, p. 1404-1411.

Research output: Contribution to journalArticle

Baffert, Carole ; Collomb, Marie Noëlle ; Deronzier, Alain ; Pécaut, Jacques ; Limburg, Julian ; Crabtree, Robert H. ; Brudvig, Gary W. / Two new terpyridine dimanganese complexes : A manganese(III,III) complex with a single unsupported oxo bridge and a manganese(III,IV) complex with a dioxo bridge. Synthesis, structure, and redox properties. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 6. pp. 1404-1411.
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abstract = "Two new terpyridine dimanganese oxo complexes [Mn2III,IV(μ-O)2(terpy)2(CF 3CO2)2]+ (3) and [Mn2III,III(μ-O)(terpy)2-(CF 3CO2)4] (4) (terpy = 2,2′:6,2″-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn2III,IV(μ-O)2(terpy)2(H 2O)2]3+ (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF3CO2- ligands on each manganese adopt a cis geometry to each other; one CF3CO2- is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF3CO2- have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH3CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH3CN solution into the mixed-valent complex 3 and the mononuclear complex [MnIIterpy)2]2+ (2), thereby preventing the observation of its electrochemical behavior.",
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T1 - Two new terpyridine dimanganese complexes

T2 - A manganese(III,III) complex with a single unsupported oxo bridge and a manganese(III,IV) complex with a dioxo bridge. Synthesis, structure, and redox properties

AU - Baffert, Carole

AU - Collomb, Marie Noëlle

AU - Deronzier, Alain

AU - Pécaut, Jacques

AU - Limburg, Julian

AU - Crabtree, Robert H.

AU - Brudvig, Gary W

PY - 2002/3/25

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N2 - Two new terpyridine dimanganese oxo complexes [Mn2III,IV(μ-O)2(terpy)2(CF 3CO2)2]+ (3) and [Mn2III,III(μ-O)(terpy)2-(CF 3CO2)4] (4) (terpy = 2,2′:6,2″-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn2III,IV(μ-O)2(terpy)2(H 2O)2]3+ (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF3CO2- ligands on each manganese adopt a cis geometry to each other; one CF3CO2- is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF3CO2- have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH3CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH3CN solution into the mixed-valent complex 3 and the mononuclear complex [MnIIterpy)2]2+ (2), thereby preventing the observation of its electrochemical behavior.

AB - Two new terpyridine dimanganese oxo complexes [Mn2III,IV(μ-O)2(terpy)2(CF 3CO2)2]+ (3) and [Mn2III,III(μ-O)(terpy)2-(CF 3CO2)4] (4) (terpy = 2,2′:6,2″-terpyridine) have been synthesized and their X-ray structures determined. In contrast to the corresponding mixed-valent aqua complex [Mn2III,IV(μ-O)2(terpy)2(H 2O)2]3+ (1), the two Mn atoms in 3 are not crystallographically equivalent. The neutral binuclear monooxo manganese(III,III) complex 4 exhibits two crystallographic forms having cis and trans configurations. In the cis complex, the two CF3CO2- ligands on each manganese adopt a cis geometry to each other; one CF3CO2- is trans to the oxygen of the oxo bridge while the second is cis. In the trans complex, the two coordinated CF3CO2- have a trans geometry to each other and are cis to the oxo bridge. The electrochemical behavior of 3 in organic medium (CH3CN) shows that this complex could be oxidized into its corresponding stable manganese(IV,IV) species while its reduced form manganese(III,III) is very unstable and leads by a disproportionation process to Mn(II) and Mn(IV) complexes. Complex 4 is only stable in the solid state, and it disproportionates spontaneously in CH3CN solution into the mixed-valent complex 3 and the mononuclear complex [MnIIterpy)2]2+ (2), thereby preventing the observation of its electrochemical behavior.

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