Ruthenium(III) acetylacetonate is a coordination complex with the formula Ru(O2C5H7)3. O2C5H7− is the ligand called acetylacetonate. This compound exists as a dark violet solid that is soluble in most organic solvents.[3] It is used as a precursor to other compounds of ruthenium.
In 1914 tris(acetylacetonato)ruthenium (III) was first prepared by the reaction of ruthenium(III) chloride and acetylacetone in the presence of potassium bicarbonate.[4] Since then, alternative synthetic routes have been examined, but the original procedure remains useful with minor variations:[5]
This compound has idealized D3 symmetry. Six oxygen atoms surround the central ruthenium atom in an octahedral arrangement. The average Ru-O bond length in Ru(acac)3 is 2.00 Å.[1] Because Ru(acac)3 is low spin, there is one unpaired d electron, causing this compound to be paramagnetic. Ru(acac)3 has a magnetic susceptibility, χM, of 3.032×10−6 cm3/mol with an effective magnetic moment, μeff, of 1.66 μB.[6] As a solution in dimethylformamide, the compound oxidizes at 0.593 and reduces at -1.223 V vs the ferrocene/ferrocenium couple.[7]
Reduction of Ru(acac)3 in the presence of alkenes affords the related diolefin complexes. Typically, such reactions are conducted with zincamalgam in moist tetrahydrofuran:[8]
The resulting compounds are rare examples of metal-alkene complexes that reversibly sustain oxidation:
Ru(acac)2(alkene)2 ⇌ [Ru(acac)2(alkene)2]+ + e−
The complex has been resolved into individual enantiomers by separation of its adduct with dibenzoyltartaric acid.[9]
ReferencesEdit
^ abChao, G.; Sime, R. L.; Sime, R. J. (1973). "Crystal and molecular structure of tris(acetylacetonato)ruthenium(III)". Acta Crystallographica B. 29 (12): 2845. doi:10.1107/S0567740873007636.
^R. C. Mehrotra, R. Bohra, and D.P. Gaur "Metal β-Diketonates and Allied Derivatives", 1st ed.; Academic Press inc.: New York, 1978. ISBN0-12-488150-5.
^Barbieri, G. A. (1914). "Systematic chemical investigations: ruthenium, rhodium, palladium". Atti Accad, Lincei. 23 (1): 334–40.
^Gupta, A. (2000). "Improved synthesis and reactivity of tris(acetylacetonato)ruthenium(III)". Indian Journal of Chemistry, Section A. 39A (4): 457. ISSN 0376-4710.
^Grobelny, R. (1966). "The absorption spectra and magnetic properties of the chelated compounds of Ru(III) with β-diketones". Journal of Inorganic and Nuclear Chemistry. 28 (11): 2715–2718. doi:10.1016/0022-1902(66)80398-6.
^Paul Sharpe; N. George Alameddin; David E. Richardson (1994). "Alkyl Substituent Effects in the Redox Thermochemistry of Coordination Compounds: Oxidation and Reduction Energetics for Ruthenium Tris(β-diketonate) Complexes in Solution and the Gas Phase". Journal of the American Chemical Society. 116 (24): 11098–11108. doi:10.1021/ja00103a027.
^Bennett, M. A.; Byrnes, Matthew J.; Kováčik, Ivan (2004). "The fragment bis(acetylacetonato)ruthenium: a meeting-point of coordination and organometallic chemistry". Journal of Organometallic Chemistry. 689 (24): 4463. doi:10.1016/j.jorganchem.2004.07.027.
^Drake, A. F.; Gould, J. M.; Mason, S. F.; Rosini, C.; Woodley, F. J. (1983). "The optical resolution of tris(pentane-2,4-dionato)metal(III) complexes". Polyhedron. 2 (6): 537–538. doi:10.1016/S0277-5387(00)87108-9.
August 29, 2023
ruthenium, acetylacetonate, coordination, complex, with, formula, o2c5h7, o2c5h7, ligand, called, acetylacetonate, this, compound, exists, dark, violet, solid, that, soluble, most, organic, solvents, used, precursor, other, compounds, ruthenium, namesiupac, na. Ruthenium III acetylacetonate is a coordination complex with the formula Ru O2C5H7 3 O2C5H7 is the ligand called acetylacetonate This compound exists as a dark violet solid that is soluble in most organic solvents 3 It is used as a precursor to other compounds of ruthenium Ruthenium III acetylacetonate NamesIUPAC name Tris acetylacetonato Ruthenium III Other names Ru acac 3 Ruthenium III 2 4 Pentanedionate Ruthenium III acetylacetonato 2 4 pentanedione ruthenium III IdentifiersCAS Number 14284 93 6 Y3D model JSmol Interactive imageECHA InfoCard 100 034 705EC Number 238 193 0PubChem CID 16057901CompTox Dashboard EPA DTXSID10904287InChI InChI 1S 3C5H8O2 Ru c3 1 4 6 3 5 2 7 h3 3H2 1 2H3 Key GNHBILLJFGEMKL UHFFFAOYSA NSMILES CC O CC O C CC O CC O C CC O CC O C Ru PropertiesChemical formula C5H7O2 3RuMolar mass 398 39 g molAppearance Dark violet solidDensity 1 54 g cm3 1 Melting point 260 C 500 F 533 K Solubility in water insoluble in waterSolubility soluble in most organic solventsHazards 2 GHS labelling PictogramsSignal word WarningHazard statements H302 H315 H319 H335 H413Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox referencesPreparation EditIn 1914 tris acetylacetonato ruthenium III was first prepared by the reaction of ruthenium III chloride and acetylacetone in the presence of potassium bicarbonate 4 Since then alternative synthetic routes have been examined but the original procedure remains useful with minor variations 5 RuCl3 3H2O MeCOCH2COMe Ru acac 3 3 HCl 3 H2OStructure and properties EditThis compound has idealized D3 symmetry Six oxygen atoms surround the central ruthenium atom in an octahedral arrangement The average Ru O bond length in Ru acac 3 is 2 00 A 1 Because Ru acac 3 is low spin there is one unpaired d electron causing this compound to be paramagnetic Ru acac 3 has a magnetic susceptibility xM of 3 032 10 6 cm3 mol with an effective magnetic moment meff of 1 66 mB 6 As a solution in dimethylformamide the compound oxidizes at 0 593 and reduces at 1 223 V vs the ferrocene ferrocenium couple 7 Reduction of Ru acac 3 in the presence of alkenes affords the related diolefin complexes Typically such reactions are conducted with zinc amalgam in moist tetrahydrofuran 8 2 Ru acac 3 4 alkene Zn 2 Ru acac 2 alkene 2 Zn acac 2The resulting compounds are rare examples of metal alkene complexes that reversibly sustain oxidation Ru acac 2 alkene 2 Ru acac 2 alkene 2 e The complex has been resolved into individual enantiomers by separation of its adduct with dibenzoyltartaric acid 9 References Edit a b Chao G Sime R L Sime R J 1973 Crystal and molecular structure of tris acetylacetonato ruthenium III Acta Crystallographica B 29 12 2845 doi 10 1107 S0567740873007636 C amp L Inventory echa europa eu R C Mehrotra R Bohra and D P Gaur Metal b Diketonates and Allied Derivatives 1st ed Academic Press inc New York 1978 ISBN 0 12 488150 5 Barbieri G A 1914 Systematic chemical investigations ruthenium rhodium palladium Atti Accad Lincei 23 1 334 40 Gupta A 2000 Improved synthesis and reactivity of tris acetylacetonato ruthenium III Indian Journal of Chemistry Section A 39A 4 457 ISSN 0376 4710 Grobelny R 1966 The absorption spectra and magnetic properties of the chelated compounds of Ru III with b diketones Journal of Inorganic and Nuclear Chemistry 28 11 2715 2718 doi 10 1016 0022 1902 66 80398 6 Paul Sharpe N George Alameddin David E Richardson 1994 Alkyl Substituent Effects in the Redox Thermochemistry of Coordination Compounds Oxidation and Reduction Energetics for Ruthenium Tris b diketonate Complexes in Solution and the Gas Phase Journal of the American Chemical Society 116 24 11098 11108 doi 10 1021 ja00103a027 Bennett M A Byrnes Matthew J Kovacik Ivan 2004 The fragment bis acetylacetonato ruthenium a meeting point of coordination and organometallic chemistry Journal of Organometallic Chemistry 689 24 4463 doi 10 1016 j jorganchem 2004 07 027 Drake A F Gould J M Mason S F Rosini C Woodley F J 1983 The optical resolution of tris pentane 2 4 dionato metal III complexes Polyhedron 2 6 537 538 doi 10 1016 S0277 5387 00 87108 9 Retrieved from https en wikipedia org w index php title Ruthenium III acetylacetonate amp oldid 1152386762, wikipedia, wiki, book, books, library,
