The fragment bis(acetylacetonato)ruthenium: A meeting-point of coordination and organometallic chemistry

Martin A. Bennett; Matthew J. Byrnes; Ivan Kováčik

doi:10.1016/j.jorganchem.2004.07.027

The fragment bis(acetylacetonato)ruthenium: A meeting-point of coordination and organometallic chemistry

Martin A. Bennett, Matthew J. Byrnes, Ivan Kováčik

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Abstract

The classical coordination compound tris(acetylacetonato)ruthenium(III), Ru(acac)₃, is a useful precursor to a range of coordination and organometallic complexes containing the fragment Ru(acac)₂ in which the metal atom displays the oxidation states +2 and +3. The review summarizes work on the alkene and alkyne complexes, in particular, the behaviour of the ruthenium(III) compounds towards nucleophiles. Reduction of [Ru(acac) ₃] with zinc in THF/H₂O provides a range of coordination and organometallic complexes containing Ru^II(acac)₂, whose chemistry is reviewed. Most of these compounds, including those containing alkenes, undergo reversible one-electron oxidation to their Ru ^III(acac)₂ counterparts, and the alkene-ruthenium(III) cations have been detected by spectroelectrochemistry. The cations derived from the chelate N-donor ligands o-CH₂CHC₆H₄NMe ₂ and o-PhCCC₆H₄NMe₂ have been isolated and structurally characterized. Comparison of the metrical data establishes that, whereas the alkene is less firmly bound to Ru^III than to Ru^II, the alkyne is bound about as strongly to Ru ^III as to Ru^II. Some uncharged nucleophiles (pyridine, diethylamine, PPh₃) react with the cationic Ru^III complexes to give unusual, paramagnetic Ru^III-C σ-bonded chelate complexes.

Original language	English
Pages (from-to)	4463-4474
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	24 SPEC. ISS.
DOIs	https://doi.org/10.1016/j.jorganchem.2004.07.027
Publication status	Published - 29 Nov 2004

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10.1016/j.jorganchem.2004.07.027

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title = "The fragment bis(acetylacetonato)ruthenium: A meeting-point of coordination and organometallic chemistry",

abstract = "The classical coordination compound tris(acetylacetonato)ruthenium(III), Ru(acac)3, is a useful precursor to a range of coordination and organometallic complexes containing the fragment Ru(acac)2 in which the metal atom displays the oxidation states +2 and +3. The review summarizes work on the alkene and alkyne complexes, in particular, the behaviour of the ruthenium(III) compounds towards nucleophiles. Reduction of [Ru(acac) 3] with zinc in THF/H2O provides a range of coordination and organometallic complexes containing RuII(acac)2, whose chemistry is reviewed. Most of these compounds, including those containing alkenes, undergo reversible one-electron oxidation to their Ru III(acac)2 counterparts, and the alkene-ruthenium(III) cations have been detected by spectroelectrochemistry. The cations derived from the chelate N-donor ligands o-CH2CHC6H4NMe 2 and o-PhCCC6H4NMe2 have been isolated and structurally characterized. Comparison of the metrical data establishes that, whereas the alkene is less firmly bound to RuIII than to RuII, the alkyne is bound about as strongly to Ru III as to RuII. Some uncharged nucleophiles (pyridine, diethylamine, PPh3) react with the cationic RuIII complexes to give unusual, paramagnetic RuIII-C σ-bonded chelate complexes.",

keywords = "Acetylacetonate, Alkene complexes, Alkyne complexes, Nucleophilic attack, Redox behaviour, Ruthenium",

author = "Bennett, {Martin A.} and Byrnes, {Matthew J.} and Ivan Kov{\'a}{\v c}ik",

year = "2004",

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T1 - The fragment bis(acetylacetonato)ruthenium

T2 - A meeting-point of coordination and organometallic chemistry

AU - Bennett, Martin A.

AU - Byrnes, Matthew J.

AU - Kováčik, Ivan

PY - 2004/11/29

Y1 - 2004/11/29

N2 - The classical coordination compound tris(acetylacetonato)ruthenium(III), Ru(acac)3, is a useful precursor to a range of coordination and organometallic complexes containing the fragment Ru(acac)2 in which the metal atom displays the oxidation states +2 and +3. The review summarizes work on the alkene and alkyne complexes, in particular, the behaviour of the ruthenium(III) compounds towards nucleophiles. Reduction of [Ru(acac) 3] with zinc in THF/H2O provides a range of coordination and organometallic complexes containing RuII(acac)2, whose chemistry is reviewed. Most of these compounds, including those containing alkenes, undergo reversible one-electron oxidation to their Ru III(acac)2 counterparts, and the alkene-ruthenium(III) cations have been detected by spectroelectrochemistry. The cations derived from the chelate N-donor ligands o-CH2CHC6H4NMe 2 and o-PhCCC6H4NMe2 have been isolated and structurally characterized. Comparison of the metrical data establishes that, whereas the alkene is less firmly bound to RuIII than to RuII, the alkyne is bound about as strongly to Ru III as to RuII. Some uncharged nucleophiles (pyridine, diethylamine, PPh3) react with the cationic RuIII complexes to give unusual, paramagnetic RuIII-C σ-bonded chelate complexes.

AB - The classical coordination compound tris(acetylacetonato)ruthenium(III), Ru(acac)3, is a useful precursor to a range of coordination and organometallic complexes containing the fragment Ru(acac)2 in which the metal atom displays the oxidation states +2 and +3. The review summarizes work on the alkene and alkyne complexes, in particular, the behaviour of the ruthenium(III) compounds towards nucleophiles. Reduction of [Ru(acac) 3] with zinc in THF/H2O provides a range of coordination and organometallic complexes containing RuII(acac)2, whose chemistry is reviewed. Most of these compounds, including those containing alkenes, undergo reversible one-electron oxidation to their Ru III(acac)2 counterparts, and the alkene-ruthenium(III) cations have been detected by spectroelectrochemistry. The cations derived from the chelate N-donor ligands o-CH2CHC6H4NMe 2 and o-PhCCC6H4NMe2 have been isolated and structurally characterized. Comparison of the metrical data establishes that, whereas the alkene is less firmly bound to RuIII than to RuII, the alkyne is bound about as strongly to Ru III as to RuII. Some uncharged nucleophiles (pyridine, diethylamine, PPh3) react with the cationic RuIII complexes to give unusual, paramagnetic RuIII-C σ-bonded chelate complexes.

KW - Acetylacetonate

KW - Alkene complexes

KW - Alkyne complexes

KW - Nucleophilic attack

KW - Redox behaviour

KW - Ruthenium

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DO - 10.1016/j.jorganchem.2004.07.027

M3 - Article

SN - 0022-328X

VL - 689

SP - 4463

EP - 4474

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 24 SPEC. ISS.

ER -

The fragment bis(acetylacetonato)ruthenium: A meeting-point of coordination and organometallic chemistry

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