| Revision as of 04:01, 13 August 2011 editSmokefoot (talk | contribs)Autopatrolled, Extended confirmed users, Pending changes reviewers, Rollbackers74,610 editsm moved Tris(acetylacetonato) iron(III) to Tris(acetylacetonato)iron(III): conv spelling← Previous edit |
Latest revision as of 16:26, 24 October 2024 edit undo205.208.121.243 (talk) →Structure and properties |
| (57 intermediate revisions by 35 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
|Watchedfields = changed |
|
| verifiedrevid = 401205847 |
|
|
|
|verifiedrevid = 444564832 |
|
| ImageFile1 = Structure of Fe(acac)3.png |
|
|
|
|ImageFile1 = Tris(acetylacetonato)iron(III)-2D-by-AHRLS-2012.png |
|
| ImageSize1 = 180px |
|
|
|
|ImageSize1 = 150px |
|
| ImageFile2 = |
|
|
|
|ImageFile2 = Iron acetylacetonate complex ball.png |
|
| ImageSize2 = |
|
|
|
|ImageSize2 = 150px |
|
| IUPACName = Tris(acetylacetonato)Iron (III) |
|
|
|
|ImageFile3 = Sample of Fe(acac)3.JPG |
|
| OtherNames = Iron(III) acetylacetonate, Iron(III) tris(2,4-pentanedionato), Fe(acac)<sub>3</sub> |
|
|
|
|ImageSize3 = 150px |
|
| Section1 = {{Chembox Identifiers |
|
|
|
|IUPACName = Tris(2,4-dioxopentan-3-ido-κ<sup>2</sup>''O'',''O''′)iron |
|
| Abbreviations = |
|
|
|
|OtherNames = Iron(III) acetylacetonate, Iron(III) tris(2,4-pentanedionato), Fe(acac)<sub>3</sub> |
|
| CASNo = 14024-18-1 |
|
|
|
|Section1={{Chembox Identifiers |
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|
|
|CASNo = 14024-18-1 |
|
| EINECS = |
|
|
|
|CASNo_Ref = {{cascite|correct|CAS}} |
|
| PubChem = |
|
|
|
|UNII_Ref = {{fdacite|correct|FDA}} |
|
| SMILES = |
|
|
|
|UNII = 118BHF260P |
|
| InChI = |
|
|
|
|ChemSpiderID = 4588230 |
|
| RTECS = |
|
|
|
|EINECS = 237-853-5 |
|
| MeSHName = |
|
|
|
|PubChem = 139087805 |
|
| ChEBI_Ref = {{ebicite|correct|EBI}} |
|
|
|
|SMILES = CC(=C(C)O1)O123(OC(=C(C)O2)C)OC(=C(C)O3)C |
|
| ChEBI = |
|
|
|
|StdInChI=1S/3C5H8O2.Fe/c3*1-4(6)3-5(2)7;/h3*3,6H,1-2H3;/q;;;+3/p-3/b3*4-3-; |
|
| KEGG_Ref = {{keggcite|correct|kegg}} |
|
|
|
|StdInChIKey = AQBLLJNPHDIAPN-LNTINUHCSA-K |
|
| KEGG = |
|
|
| ATCCode_prefix = |
|
|
| ATCCode_suffix = |
|
|
| ATC_Supplemental =}} |
|
|
| Section2 = {{Chembox Properties |
|
|
| Formula = Fe(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>3</sub> |
|
|
| Appearance = Red Solid |
|
|
| Density = 5.24 g/cm<sup>3</sup> |
|
|
| MeltingPt = 180-181 °C |
|
|
| Melting_notes = |
|
|
| BoilingPt = 100 °C |
|
|
| Boiling_notes = at 13.00 hPa |
|
|
| Solubility = 2 g/L |
|
|
| SolubleOther = |
|
|
| = |
|
|
| pKa = |
|
|
| pKb = }} |
|
|
| Section7 = {{Chembox Hazards |
|
|
| EUClass = |
|
|
| EUIndex = |
|
|
| MainHazards = |
|
|
| NFPA-H = |
|
|
| NFPA-F = |
|
|
| NFPA-R = |
|
|
| NFPA-O = |
|
|
| RPhrases = {{R22}}, {{R36}} |
|
|
| SPhrases = {{S26}} |
|
|
| RSPhrases = |
|
|
| FlashPt = |
|
|
| Autoignition = |
|
|
| ExploLimits = |
|
|
| PEL = }} |
|
|
}} |
|
}} |
|
|
|Section2={{Chembox Properties |
|
|
|Formula = Fe(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>3</sub> |
|
|
|Appearance = Red Solid |
|
|
|Density = 1.348 g/cm<sup>3</sup> |
|
|
|MolarMass = 353.17 g/mol |
|
|
|MeltingPtC = 180 to 181 |
|
|
|BoilingPt = decomposes |
|
|
|Solubility = 2 g/L |
|
|
}} |
|
|
|Section7={{Chembox Hazards |
|
|
|GHSPictograms = {{GHS05}} {{GHS07}} |
|
|
|GHSSignalWord = Danger |
|
|
|HPhrases = {{H-phrases|H302 + H312 + H332 | H318}} |
|
|
|PPhrases = {{P-phrases|P261 | P280 | P301 + P312 | P302 + P352 + P312 | P304 + P340 + P312 | P305 + P351 + P338}} |
|
|
|GHS_ref = <ref>GHS: </ref> |
|
|
}} |
|
|
}} |
|
|
] |
|
|
|
|
|
'''Tris(acetylacetonato) iron(III)''', often abbreviated Fe(acac)<sub>3</sub>, is a ] ] featuring ] (acac) ]s. It is a red air-stable solid that dissolves in nonpolar organic solvents. |
|
'''Tris(acetylacetonato) iron(III)''', often abbreviated Fe(acac)<sub>3</sub>, is a ] ] featuring ] (acac) ]s, making it one of a family of ]. It is a red air-stable solid that dissolves in nonpolar organic solvents. |
|
|
|
|
|
==Preparation== |
|
==Preparation== |
|
Fe(acac)<sub>3</sub> is prepared by treating freshly precipitated Fe(OH)<sub>3</sub> with ], forming deep red crystals of Fe(acac)<sub>3</sub>.<ref>{{US patent reference |
|
Fe(acac)<sub>3</sub> is prepared by treating freshly precipitated Fe(OH)<sub>3</sub> with ].<ref>{{US patent reference| number = 2004127690| y = 2004| m = 07| d = 01| inventor = Chaudhari, Mihir Kanti et al.| title = Process for making metal acetylacetonates}}</ref> |
|
|
:Fe(OH)<sub>3</sub> + 3 HC<sub>5</sub>H<sub>7</sub>O<sub>2</sub> → Fe(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>3</sub> + 3 H<sub>2</sub>O |
|
| number = 2004012769 |
|
|
| y = 2004 |
|
|
| m = 07 |
|
|
| d = 01 |
|
|
| inventor = Chaudhari, Mihir Kanti et al |
|
|
| title = Process for making metal acetylacetonates |
|
|
}}</ref> |
|
|
:Fe(OH)<sub>3</sub> + 3 C<sub>5</sub>H<sub>8</sub>O<sub>2</sub> → Fe(acac)<sub>3</sub> + 3 H<sub>2</sub>O |
|
|
|
|
|
|
==Structure and properties== |
|
==Structure and properties== |
|
|
Fe(acac)<sub>3</sub> is an octahedral complex with six equivalent Fe-O bonds with bond distances of about 2.00 Å. The regular geometry is consistent with a ] Fe<sup>3+</sup> core with sp3d2 hybridization. As the metal orbitals are all evenly occupied the complex is not subject to ] and thus adopts a D<sub>3</sub> ]. In contrast, the related metal acetylacetonate Mn(acac)<sub>3</sub> adopts a more distorted octahedral structure.<ref>{{cite journal | title = The infrared absorption spectra of metal acetylacetonates. | author = Lawson, K.E. | journal = Spectrochimica Acta | year = 1961 | volume = 17 | issue = 3| pages = 248–258 | doi = 10.1016/0371-1951(61)80071-4| bibcode = 1961AcSpe..17..248L }}</ref> The 5 unpaired ''d''-electrons also result in the complex being ], with a ] of 5.90 μ<sub>B</sub>. |
|
Fe(acac)<sub>3</sub> is a ] compound with a magnetic moment of 5.90 μ<sub>B</sub>. This homoleptic metal acetylacetonate has an octahedral geometry with D<sub>3</sub> ], with no apparent Jahn-Teller distortions, unlike related metal acetylacetonate Mn(acac)<sub>3</sub>.<ref>{{cite journal |
|
|
| title = The infrared absorption spectra of metal acetylacetonates. |
|
|
| author = Lawson, K.E. |
|
|
| journal = Spectrochimica Acta |
|
|
| year = 1961 |
|
|
| volume = 17 |
|
|
| issue = |
|
|
| pages = 248–258 |
|
|
| doi = 10.1016/0371-1951(61)80071-4 |
|
|
}}</ref> |
|
|
|
|
|
|
|
Fe(acac)<sub>3</sub> possesses ]. The Δ- and Λ-]s slowly inter-convert via ] and ]s. The rate of interconversion is sufficiently slow to allow its enantiomers to be partially resolved.<ref>Anders Lennartson "Optical resolution and racemisation of " Inorganica Chimica Acta 2011, vol. 365, pp. 451–453. {{doi|10.1016/j.ica.2010.07.066}}</ref> |
|
==Applications== |
|
|
|
|
|
Fe(acac)<sub>3</sub> has been exploited as a catalyst and reagent in organic chemistry, especially for reactions involving ]. Not only being useful in catalysis, Fe(acac)<sub>3</sub> can be reactive. In one instance, Fe(acac)<sub>3</sub> is used to form an intermediate en-route to the carbon-carbon bond forming reaction of cross-coupling a ] to an ].<ref>{{cite journal |
|
|
|
==Reactions== |
|
| title = Iron-Catalyzed Aminohydroxylation of Olefins |
|
|
|
Fe(acac)<sub>3</sub> has been examined as a precatalyst and reagent in organic chemistry, although the active iron-containing species is usually unidentified in these processes. In one instance, Fe(acac)<sub>3</sub> was shown to promote cross-coupling a ] to an ].<ref>{{cite journal| title = Iron-Catalyzed Aminohydroxylation of Olefins|author1=Takacs, J. A., L. |author2=Madhavan, G.V. |author3=Creswell, M. |author4=Seely, F. |author5=Devroy, W. | journal = Organometallics| year = 1986| volume = 5| issue = 11| pages = 2395–2398| doi = 10.1021/om00142a044}}</ref> Fe(acac)<sub>3</sub> catalyzes the dimerization of ] to a mixture of 1,5-dimethyl-1,5-cyclooctadiene and 2,5-dimethyl-1,5-cyclooctadiene.<ref>{{cite journal| title = Oligomerization of isoprene by cobalt or iron complex catalysts| author = Misono, A.| journal = Bulletin of the Chemical Society of Japan| year = 1966| volume = 39| issue = 11| pages = 2425–2429| doi=10.1246/bcsj.39.2425 | doi-access = free}}</ref> |
|
| author = Takacs, J. A., L.; Madhavan, G.V.; Creswell, M.; Seely, F.; Devroy, W. |
|
|
| journal = Organometallics |
|
|
| year = 1986 |
|
|
| volume = 5 |
|
|
| issue = 11 |
|
|
| pages = 2395–2398 |
|
|
| doi = 10.1021/om00142a044 |
|
|
}}</ref> For instance, Fe(acac)<sub>3</sub> catalyzes the dimerization of ] to a mixture of 1,5-dimethyl-1,5-cyclooctadiene and 2,5-dimethyl-1,5-cyclooctadiene.<ref>{{cite journal |
|
|
| title = Oligomerization of isoprene by cobalt or iron complex catalysts. |
|
|
| author = Misono, A. |
|
|
| journal = Bulletin of the Chemical Society of Japan |
|
|
| year = 1966 |
|
|
| volume = 39 |
|
|
| issue = 11 |
|
|
| pages = 2425 |
|
|
| doi =10.1246/bcsj.39.2425 |
|
|
}}</ref> |
|
|
:] |
|
:] |
|
|
|
|
|
Fe(acac)<sub>3</sub> also catalyzes the ring-opening polymerization of 1,3-benzoxazine.<ref>{{cite journal |
|
Fe(acac)<sub>3</sub> also catalyzes the ring-opening polymerization of 1,3-benzoxazine.<ref>{{cite journal |
|
|
| title = Highly efficient catalysts-acetylacetonato complexes of transition metals in the 4th period for ring-opening polymerization of 1,3-benzoxazine| first3 = Takeshi| last3 = Endo| first2 = Shoji| last2 =Hirayama | author = Sudo, A.| journal = Journal of Polymer Science Part A: Polymer Chemistry| year = 2010| volume = 48| issue = 2| pages = 479| doi = 10.1002/pola.23810| bibcode = 2010JPoSA..48..479S}}</ref> Beyond the area of polymerization, Fe(acac)<sub>3</sub> has been found to catalyze the reaction of ] with olefins to form 1,3-oxazolidine products.<ref>{{cite journal| title = Iron-Catalyzed Aminohydroxylation of Olefins|author1=Williamson, K. T. |author2=Yoon, T. | journal = J. Am. Chem. Soc.| year = 2010| volume = 132| pmid = 20232850| issue = 13| pages = 4570–4571| pmc = 2857537| doi = 10.1021/ja1013536}}</ref> |
|
| title = Highly efficient catalysts-acetylacetonato complexes of transition metals in the 4th period for ring-opening polymerization of 1,3-benzoxazine |
|
|
| first3 = Takeshi |
|
|
| last3 = Endo |
|
|
| first2 = Shoji |
|
|
| last2 = Hirayama |
|
|
| author = Sudo, A. |
|
|
| journal = Journal of polymer science. Part A, Polymer chemistry |
|
|
| year = 2010 |
|
|
| volume = 48 |
|
|
| issue = 2 |
|
|
| pages = 479 |
|
|
| doi = 10.1002/pola.23810 |
|
|
}}</ref> Beyond the area of polymerization, Fe(acac)<sub>3</sub> has been found to catalyze the reaction of ] with olefins to form 1,3-oxazolidine products.<ref>{{cite journal |
|
|
| title = Iron-Catalyzed Aminohydroxylation of Olefins |
|
|
| author = Williamson, K. T.; Yoon, T. |
|
|
| journal = J. Am. Chem. Soc. |
|
|
| year = 2010 |
|
|
| volume = 132 |
|
|
| pmid = 20232850 |
|
|
| issue = 13 |
|
|
| pages = 4570–4571 |
|
|
| pmc = 2857537 |
|
|
| doi = 10.1021/ja1013536 |
|
|
}}</ref> |
|
|
:] |
|
:] |
|
|
|
|
| Line 131: |
Line 63: |
|
{{reflist}} |
|
{{reflist}} |
|
|
|
|
|
] |
|
{{Iron compounds}} |
|
|
{{Acetylacetonate complexes}} |
|
|
|
|
|
] |
|
] |
|
] |
|
|
] |