[{"@context":"http:\/\/schema.org\/","@type":"BlogPosting","@id":"https:\/\/wiki.edu.vn\/en\/wiki19\/nickelii-bisacetylacetonate-wikipedia\/#BlogPosting","mainEntityOfPage":"https:\/\/wiki.edu.vn\/en\/wiki19\/nickelii-bisacetylacetonate-wikipedia\/","headline":"Nickel(II) bis(acetylacetonate) – Wikipedia","name":"Nickel(II) bis(acetylacetonate) – Wikipedia","description":"From Wikipedia, the free encyclopedia Coordination complex Nickel(II) bis(acetylacetonate) Names Other names Ni(acac)2, nickel acac Identifiers ChemSpider ECHA InfoCard 100.019.887","datePublished":"2016-02-14","dateModified":"2016-02-14","author":{"@type":"Person","@id":"https:\/\/wiki.edu.vn\/en\/wiki19\/author\/lordneo\/#Person","name":"lordneo","url":"https:\/\/wiki.edu.vn\/en\/wiki19\/author\/lordneo\/","image":{"@type":"ImageObject","@id":"https:\/\/secure.gravatar.com\/avatar\/c9645c498c9701c88b89b8537773dd7c?s=96&d=mm&r=g","url":"https:\/\/secure.gravatar.com\/avatar\/c9645c498c9701c88b89b8537773dd7c?s=96&d=mm&r=g","height":96,"width":96}},"publisher":{"@type":"Organization","name":"Enzyklop\u00e4die","logo":{"@type":"ImageObject","@id":"https:\/\/wiki.edu.vn\/wiki4\/wp-content\/uploads\/2023\/08\/download.jpg","url":"https:\/\/wiki.edu.vn\/wiki4\/wp-content\/uploads\/2023\/08\/download.jpg","width":600,"height":60}},"image":{"@type":"ImageObject","@id":"https:\/\/upload.wikimedia.org\/wikipedia\/commons\/thumb\/5\/57\/ACACNI01.png\/270px-ACACNI01.png","url":"https:\/\/upload.wikimedia.org\/wikipedia\/commons\/thumb\/5\/57\/ACACNI01.png\/270px-ACACNI01.png","height":"190","width":"270"},"url":"https:\/\/wiki.edu.vn\/en\/wiki19\/nickelii-bisacetylacetonate-wikipedia\/","about":["Wiki"],"wordCount":4842,"articleBody":"From Wikipedia, the free encyclopediaCoordination complexNickel(II) bis(acetylacetonate)NamesOther namesNi(acac)2, nickel acacIdentifiersChemSpiderECHA InfoCard100.019.887 EC NumberUNIIInChI=1S\/2C5H8O2.Ni\/c2*1-4(6)3-5(2)7;\/h2*3,6H,1-2H3;\/b2*4-3-;Key:\u00a0SHWZFQPXYGHRKT-FDGPNNRMSA-NC\/C(=C\/C(=O)C)\/O.C\/C(=C\/C(=O)C)\/O.[Ni]PropertiesC30H42Ni3O12Molar mass770.734\u00a0g\u00b7mol\u22121Appearancedark greenDensity1.455 g\/cm3Melting point229.5\u00a0\u00b0C (445.1\u00a0\u00b0F; 502.6\u00a0K) (decomposes)H2OHazardsGHS labelling:DangerH302, H317, H334, H350P201, P202, P261, P264, P270, P272, P280, P281, P285, P301+P312, P302+P352, P304+P341, P308+P313, P321, P330, P333+P313, P342+P311, P363, P405, P501Except where otherwise noted, data are given for materials in their standard state (at 25\u00a0\u00b0C [77\u00a0\u00b0F], 100\u00a0kPa).Chemical compoundNickel(II) bis(acetylacetonate) is a coordination complex with the formula [Ni(acac)2]3, where acac is the anion C5H7O2\u2212 derived from deprotonation of acetylacetone. It is a dark green paramagnetic solid that is soluble in organic solvents such as toluene. It reacts with water to give the blue-green diaquo complex Ni(acac)2(H2O)2.[1]Table of ContentsStructure and properties[edit]Dihydrate[edit]Synthesis[edit]Reactions[edit]Applications[edit]See also[edit]References[edit]Structure and properties[edit]Anhydrous nickel(II) acetylacetonate exists as molecules of Ni3(acac)6. The three nickel atoms are approximately collinear and each pair of them is bridged by two \u03bc2 oxygen atoms. Each nickel atom has tetragonally distorted octahedral geometry, caused by the difference in the length of the Ni-O bonds between the bridging and non-bridging oxygens.[2] Ni3(acac)6 molecules are almost centrosymmetric, despite the non-centrosymmetric point group of the cis-Ni(acac)2 “monomers,” which is uncommon.[3] The trimeric structure allows all nickel centers to achieve an octahedral coordination. The trimer is only formed if intramolecular sharing of oxygen centers between pairs of nickel centers occurs. The anhydrous complex has interesting magnetic properties. Down to about 80\u00a0K it exhibits normal paramagnetism with an effective magnetic moment of 3.2\u00a0\u03bcB, close to the spin-only moment expected of a d8 ion with two unpaired electrons. The effective moment rises to 4.1\u00a0\u03bcB at 4.3\u00a0K, due to ferromagnetic exchange interactions involving all three nickel ions.[4]When bound to bulkier analogues of acetylacetonate ligand, steric hindrance favors formation of the mononickel derivatives.  This behavior is observed for the derivative of 3-methylacetylacetonate.[5]Dihydrate[edit]  Structure of Ni(acac)2(H2O)2.As in the anhydrous form, the Ni(II) centres occupy octahedral coordination sites.  The coordination sphere is provided by two bidentate acetylacetonate (acac) ligands and two aquo ligands.  Ni(acac)2(H2O)2 exists as cis and trans isomers.[6] Trans isomers are also observed for Ni(acac)2(pyridine-N-oxide)2.[7] In the trans isomers, the axial Ni-O bonds are greater in length (2.1000\u00c5) than the equatorial Ni-O bonds (2.0085 \u00c5 and 1.9961\u00c5).[8]  Trans and cis isomers of [Ni(acac)2X2] where X is a coordinating moleculeSynthesis[edit]Bis(2,4-pentanedionato)nickel(II) is prepared by treating nickel nitrate with acetylacetone in the presence of base. The product is the blue-green diaquo complex Ni(CH3COCHCOCH3)2(H2O)2.[9]Ni(NO3)2  +  2 CH3COCH2COCH3  +  2 H2O   + 2 NaOH   \u2192    Ni(CH3COCHCOCH3)2(H2O)2  +  2 NaNO3This complex can be dehydrated using a Dean\u2013Stark trap by azeotropic distillation:[9]3 Ni(CH3COCHCOCH3)2(H2O)2   \u2192   [Ni(CH3COCHCOCH3)2]3  +  6 H2OUpon heating Ni(acac)2(H2O)2 at 170\u2013210\u00a0\u00b0C under reduced pressure (0.2-0.4 mmHg), the anhydrous form sublimes and water is removed.[3]Reactions[edit]The anhydrous complex reacts with a range of Lewis bases to give monomeric adducts.[10]  Illustrative is the reaction with tetramethylethylenediamine (tmeda):[11][Ni(CH3COCHCOCH3)2]3 + 3 tmeda \u2192 3 Ni(CH3COCHCOCH3)2(tmeda)Ni(acac)2(H2O)2 reacts quickly in high yield at a methine positions, producing diamides from isocyanates. Related reactions occur with diethyl azodicarboxylate and dimethyl acetylenedicarboxylate:Ni(acac)2(H2O)2 + 2 PhNCO \u2192 Ni(O2C5Me2C(O)NHPh)2 + 2 H2OApplications[edit]The anhydrous complex is the precursor to nickel-based catalysts such as nickel bis(cyclooctadiene) and tetramethylethylenediamine(dimethyl)nickel(II).[12][11][Ni(acac)2]3 is a precursor for the deposition of a thin film of NiO on conductive glass substrates using sol-gel techniques.[10]  Use of “Ni(acac)2” as the precatalyst.[13]See also[edit]References[edit]^ R. C. Mehrotra; R. Bohra; D. P. Gaur (1978). Metal \u00df-Diketones and Allied Derivatives. Academic Press. ISBN\u00a00124881505.^ G. J. Bullen, R. Mason & P. Pauling (1961). “Octahedral Co-ordination of Nickel in Nickel(II) Bisacetylacetone”. Nature. 189 (4761): 291\u2013292. doi:10.1038\/189291a0. S2CID\u00a037394858.^ a b G. J. Bullen, R. Mason & P. Pauling. (1965). “The crystal and Molecular Structure of Bis(acetylacetonato)nickel (II)”. Inorganic Chemistry. 4 (4): 456\u2013462. doi:10.1021\/ic50026a005.^ Greenwood, Norman  N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd\u00a0ed.). Butterworth-Heinemann. p.\u00a01157. ISBN\u00a0978-0-08-037941-8.^ 1.  A. D\u00f6hring, R. Goddard, P. W. Jolly, C. Kr\u00fcger, V. R. Polyakov, “Monomer-Trimer Isomerism in 3-Substituted Pentane-2,4-dione Derivatives of Nickel(II)”, Inorg. Chemistry 1997, 36, 177-183. doi:10.1021\/ic960441c^ M. Kudrat-E-Zahan, Y. Nishida & H. Sakiyama (2010). “Identification of cis\/trans isomers of bis(acetylacetonato)nickel(II) complexes in solution based on electronic spectra”. Inorganica Chimica Acta. 363: 168\u2013172. doi:10.1016\/j.ica.2009.09.011.^ B. N. Figgis; M. A. Hitchman (2000). “Ligand Field Theory and its Application”. ^ O. Metin, L. T. Yildirim & S. Ozkar (2007). “Synthesis, characterization and crystal structure of bis(acetylacetonato)dimethanolnickel(II)”. Inorganic Chemistry. 10 (9): 1121\u20131123. doi:10.1016\/j.inoche.2007.06.011.^ a b Wielandt, J. W.; Ruckerbauer, D. (2010). Bis(1,5-cyclooctadiene)nickel(0). Inorganic Syntheses. Vol.\u00a035. p.\u00a0120. doi:10.1002\/9780470651568.ch6.^ a b Paul A. Williams; Anthony C. Jones; Jamie F. Bickley; Alexander Steiner; Hywel O. Davies; Timothy J. Leedham; Susan A. Impey; Joanne Garcia; Stephen Allen; Aline Rougier; Alexandra Blyr (2001). “Synthesis and Crystal Structures of Dimethylaminoethanol Adducts of Ni(II) Acetate and Ni(II) Acetylacetonate. Precursors for the Sol\u2013Gel Deposition of Electrochromic Nickel Oxide Thin Films”. Journal of Materials Chemistry. 11 (9): 2329\u20132334. doi:10.1039\/b103288g.^ a b Kaschube, Wilfried; P\u00f6rschke, Klaus R.; Wilke, G\u00fcnther (1988). “Tmeda-Nickel-Komplexe”. Journal of Organometallic Chemistry. 355 (1\u20133): 525\u2013532. doi:10.1016\/0022-328X(88)89050-8.^ G\u00f6ttker-Schnetmann, Inigo; Mecking, Stefan (2020). “A Practical Synthesis of (tmeda)Ni(CH3)2, Isotopically Labeled (tmeda)Ni(13CH3)2, and Neutral Chelated-Nickel Methyl Complexes”. Organometallics. 39 (18): 3433\u20133440. doi:10.1021\/acs.organomet.0c00500. S2CID\u00a0224930545.^ Shrestha, Ruja; Dorn, Stephanie C. M.; Weix, Daniel J. (2013-01-16). “Nickel-Catalyzed Reductive Conjugate Addition to Enones via Allylnickel Intermediates”. Journal of the American Chemical Society. 135 (2): 751\u2013762. doi:10.1021\/ja309176h. PMC\u00a03547151. PMID\u00a023270480.  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