【《过渡金属配合物活化氧气的研究文献综述》2700字】

过渡金属配合物活化氧气的研究文献综述HayaishiADDINEN.CITE<EndNote><Cite><Author>Hayaishi</Author><Year>1955</Year><RecNum>357</RecNum><DisplayText><styleface="superscript">19</style></DisplayText><record><rec-number>357</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621144386">357</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hayaishi,Osamu</author><author>Katagiri,Masayuki</author><author>Rothberg,Simon%JJournaloftheAmericanChemicalSociety</author></authors></contributors><titles><title>Mechanismofthepyrocatechasereaction</title></titles><pages>5450-5451</pages><volume>77</volume><number>20</number><dates><year>1955</year></dates><isbn>0002-7863</isbn><urls></urls></record></Cite></EndNote>19和MasonADDINEN.CITE<EndNote><Cite><Author>Mason</Author><Year>1955</Year><RecNum>356</RecNum><DisplayText><styleface="superscript">20</style></DisplayText><record><rec-number>356</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621144213">356</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mason,HS</author><author>Fowlks,WL</author><author>Peterson,E%JJournaloftheAmericanChemicalSociety</author></authors></contributors><titles><title>Oxygentransferandelectrontransportbythephenolasecomplex1</title></titles><pages>2914-2915</pages><volume>77</volume><number>10</number><dates><year>1955</year></dates><isbn>0002-7863</isbn><urls></urls></record></Cite></EndNote>20在上世纪五十年代分别发现在两种酶催化反应中氧气分子的氧原子成功转移到氧化产物中（如图1-1所示），从而揭开对过渡金属酶催化活化分子氧领域研究的序章。Mason等人发现酪氨酸酶可以将单酚转化为双酚（即儿茶酚），Hayaishi等人报道了称儿茶酚1，2-双加氧酶催化芳环裂解，氧气分子上的两个氧原子插入到底物中，得到顺式的己二烯二酸。在分子氧活化的研究之前，人们认为氧气在反应中只是充当接收电子的物种，而反应中有机底物所得到的氧原子都是从水中获取的。图1-1自然界中首次发现的氧气活化反应在此之后，人们对过渡金属酶参与的氧气活化过程进行了广泛的研究，其中血红素和非血红素酶在过渡金属活化氧气的发展过程中扮演着重要的作用。早在上世纪六十年代人们就发现血红素铁酶能够与氧气反应生成双铁的氧桥结构ADDINEN.CITE<EndNote><Cite><Author>Cohen</Author><Year>1968</Year><RecNum>359</RecNum><DisplayText><styleface="superscript">21,22</style></DisplayText><record><rec-number>359</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621144614">359</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cohen,IrwinArnold</author><author>Caughey,WinslowS%JBiochemistry</author></authors></contributors><titles><title>Substituteddeuteroporphyrins.IV.Kineticsandmechanismofreactionsofiron(II)porphyrinswithoxygen</title></titles><pages>636-641</pages><volume>7</volume><number>2</number><dates><year>1968</year></dates><isbn>0006-2960</isbn><urls></urls></record></Cite><Cite><Author>Kao</Author><Year>1965</Year><RecNum>360</RecNum><record><rec-number>360</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621144707">360</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kao,OrandaHW</author><author>Wang,JuiH%JBiochemistry</author></authors></contributors><titles><title>Kineticstudyoftheoxidationofferrohemochromebymolecularoxygen</title></titles><pages>342-347</pages><volume>4</volume><number>2</number><dates><year>1965</year></dates><isbn>0006-2960</isbn><urls></urls></record></Cite></EndNote>21,22，但是对于其中的反应机理一直存在争议。直到上世纪八十年代，人们才发现铁卟啉配合物活化氧气后首先得到过氧桥连的双铁配合物然后再通过O-O键的裂解生成四价的铁氧配合物ADDINEN.CITEADDINEN.CITE.DATA23-25（图1-2）。随后，对铁卟啉配合物活化氧气后进行的底物羟基化和环氧化反应也不断被发现ADDINEN.CITE<EndNote><Cite><Author>Takeuchi</Author><Year>1996</Year><RecNum>364</RecNum><DisplayText><styleface="superscript">26,27</style></DisplayText><record><rec-number>364</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621145361">364</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Takeuchi,Masayuki</author><author>Kodera,Masahito</author><author>Kano,Koji</author><author>Yoshida,Zen-ichi</author></authors></contributors><titles><title>Mechanismsfor(porphyrinato)iron(III)-catalyzedoxygenationofstyrenesbyO2inpresenceofBH−4</title><secondary-title>JournalofMolecularCatalysisA:Chemical</secondary-title></titles><periodical><full-title>JournalofMolecularCatalysisA:Chemical</full-title><abbr-1>J.Mol.Catal.A:Chem.</abbr-1><abbr-2>JMolCatalA:Chem</abbr-2></periodical><pages>51-59</pages><volume>113</volume><number>1-2</number><section>51</section><dates><year>1996</year></dates><isbn>13811169</isbn><urls></urls><electronic-resource-num>10.1016/s1381-1169(96)00047-7</electronic-resource-num></record></Cite><Cite><Author>Grinstaff</Author><Year>1994</Year><RecNum>365</RecNum><record><rec-number>365</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621145469">365</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Grinstaff,MarkW</author><author>Hill,MichaelG</author><author>Labinger,JayA</author><author>Gray,HarryB%JScience</author></authors></contributors><titles><title>Mechanismofcatalyticoxygenationofalkanesbyhalogenatedironporphyrins</title></titles><pages>1311-1313</pages><volume>264</volume><number>5163</number><dates><year>1994</year></dates><isbn>0036-8075</isbn><urls></urls></record></Cite></EndNote>26,27。在后续的过渡金属铁配合物活化氧气的报道中可以看出，大多数催化反应的第一步都是铁与氧气生成三价铁超氧物种（FeIII-superoxide），例如Naruta课题组ADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2009</Year><RecNum>366</RecNum><DisplayText><styleface="superscript">28</style></DisplayText><record><rec-number>366</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621145664">366</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liu,J.G.</author><author>Ohta,T.</author><author>Yamaguchi,S.</author><author>Ogura,T.</author><author>Sakamoto,S.</author><author>Maeda,Y.</author><author>Naruta,Y.</author></authors></contributors><auth-address>InstituteforMaterialsChemistryandEngineering,KyushuUniversity,Higashi-ku,Fukuoka,812-8581,Japan.</auth-address><titles><title>Spectroscopiccharacterizationofahydroperoxo-hemeintermediate:conversionofaside-onperoxotoanend-onhydroperoxocomplex</title><secondary-title>AngewChemIntEdEngl</secondary-title></titles><periodical><full-title>AngewChemIntEdEngl</full-title></periodical><pages>9262-7</pages><volume>48</volume><number>49</number><edition>2009/11/03</edition><keywords><keyword>ElectronSpinResonanceSpectroscopy</keyword><keyword>Heme/chemicalsynthesis/*chemistry</keyword><keyword>HydrogenPeroxide/chemicalsynthesis/*chemistry</keyword><keyword>MolecularStructure</keyword><keyword>SpectrumAnalysis/*methods</keyword><keyword>SpectrumAnalysis,Raman</keyword></keywords><dates><year>2009</year></dates><isbn>1521-3773(Electronic) 1433-7851(Linking)</isbn><accession-num>19882613</accession-num><urls><related-urls><url>/pubmed/19882613</url></related-urls></urls><electronic-resource-num>10.1002/anie.200904572</electronic-resource-num></record></Cite></EndNote>28以FeII(tmpIm)作为反应物，与氧气在低温下发生反应得到[FeIII(O2)(tmpIm)]，在反应中加入大量的钴酸和过量的甲醇后成功分离出Fe-OOH配合物。图1-2铁卟啉配合物参与的氧气活化反应另外锰卟啉配合物在氧气活化反应中也十分常见，上世纪七十年代Hoffman等人ADDINEN.CITE<EndNote><Cite><Author>Weschler</Author><Year>1975</Year><RecNum>367</RecNum><DisplayText><styleface="superscript">29</style></DisplayText><record><rec-number>367</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621145836">367</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Weschler,CharlesJ</author><author>Hoffman,BrianM</author><author>Basolo,Fred%JJournaloftheAmericanChemicalSociety</author></authors></contributors><titles><title>Syntheticoxygencarrier.Dioxygenadductofamanganeseporphyrin</title></titles><pages>5278-5280</pages><volume>97</volume><number>18</number><dates><year>1975</year></dates><isbn>0002-7863</isbn><urls></urls></record></Cite></EndNote>29就报道了以[MnII(TPP)(Py)]配合物在低温条件下活化氧气生成side-on构型的四价锰-过氧配合物。过渡金属锰配合物也经常被用于以氧气作为氧化剂氧化底物的反应。例如Mansuy等人ADDINEN.CITE<EndNote><Cite><Author>Battioni</Author><Year>1987</Year><RecNum>368</RecNum><DisplayText><styleface="superscript">30</style></DisplayText><record><rec-number>368</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621146140">368</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Battioni,Pierrette</author><author>Bartoli,JeanFrançois</author><author>Leduc,Philippe</author><author>Fontecave,Marc</author><author>Mansuy,Daniel%JJournaloftheChemicalSociety,ChemicalCommunications</author></authors></contributors><titles><title>Anewandefficientbiomimeticsystemforhydrocarbonoxidationbydioxygenusingmanganeseporphyrins,imidazole,andzinc</title></titles><pages>791-792</pages><number>10</number><dates><year>1987</year></dates><urls></urls></record></Cite></EndNote>30以氧气作为氧化剂，在[Mn(TPP)Cl]以1-甲基咪唑为催化剂成功实现烯烃的环氧化反应。在早期的研究中，人们对于过渡金属氧中间体的表征并不多见，且对氧化底物过程中的活性氧化剂的了解还很少。最近，Goldberg等人ADDINEN.CITE<EndNote><Cite><Author>Jung</Author><Year>2014</Year><RecNum>45</RecNum><DisplayText><styleface="superscript">31</style></DisplayText><record><rec-number>45</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1605684090">45</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jung,J.</author><author>Ohkubo,K.</author><author>Goldberg,D.P.</author><author>Fukuzumi,S.</author></authors></contributors><auth-address>DepartmentofMaterialandLifeScience,GraduateSchoolofEngineering,OsakaUniversityandALCA,JapanScienceandTechnologyAgency(JST),2-1Yamada-oka,Suita,Osaka565-0871,Japan.</auth-address><titles><title>Photocatalyticoxygenationof10-methyl-9,10-dihydroacridinebyO(2)withmanganeseporphyrins</title><secondary-title>JPhysChemA</secondary-title></titles><periodical><full-title>JPhysChemA</full-title></periodical><pages>6223-9</pages><volume>118</volume><number>32</number><edition>2014/08/01</edition><keywords><keyword>Acridines</keyword><keyword>Catalysis</keyword><keyword>Metalloporphyrins/*chemistry</keyword><keyword>Oxygen/*chemistry</keyword><keyword>PhotochemicalProcesses</keyword><keyword>QuantumTheory</keyword></keywords><dates><year>2014</year><pub-dates><date>Aug14</date></pub-dates></dates><isbn>1520-5215(Electronic) 1089-5639(Linking)</isbn><accession-num>25079061</accession-num><urls><related-urls><url>/pubmed/25079061</url></related-urls></urls><custom2>PMC4136676</custom2><electronic-resource-num>10.1021/jp505860f</electronic-resource-num></record></Cite></EndNote>31通过光催化反应活化氧气，合成并分离得到高价锰氧配合物。他们认为在光激发作用下，锰-卟啉配合物转化为被激发的三重态，然后经过单电子转移到氧气，成功活化氧气得到超氧物种(Por)MnIV(O2●-)。再通过氢原子转移过程（HAT），生成(Por)MnIV(OOH)。接下来OO键断裂得到(Por)MnV(O)配合物，在该反应中明确实现了有机底物的C-H活化过程。在过去的二十多年间，随着越来越多的非血红素酶结构和光谱数据的成功表征，涉及非血红素模型配合物的仿生学研究受到了极大的关注ADDINEN.CITE<EndNote><Cite><Author>Bruijnincx</Author><Year>2008</Year><RecNum>369</RecNum><DisplayText><styleface="superscript">32</style></DisplayText><record><rec-number>369</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621146327">369</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bruijnincx,PieterCA</author><author>vanKoten,Gerard</author><author>Gebbink,RobertusJMKlein%JChemicalSocietyReviews</author></authors></contributors><titles><title>Mononuclearnon-hemeironenzymeswiththe2-His-1-carboxylatefacialtriad:recentdevelopmentsinenzymologyandmodelingstudies</title></titles><pages>2716-2744</pages><volume>37</volume><number>12</number><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>32。但是对于反应过程中的铁氧中间体（例如FeOOH、FeO2和FeO）大多都是依赖于外部氧化剂而不是直接活化氧气所得。非血红素铁酶直接活化氧气得到铁-氧中间体的催化过程一般有两种可能的反应路径。如图1-3所示，首先是氧气和二价铁中心配位，得到三价的铁超氧物种。此时向体系中再加入质子源可进一步得到FeIIIOOH物种。FeIIIOOH物种发生的OO键断裂过程机理在许多反应中仍然不够清晰，研究人员提出了OO键均裂和异裂两种可能的断裂过程，最终得到的铁-氧物种一般是FeIV(O)物种。图1-3非血红素铁酶参与的氧气活化反应路径以过渡金属锰为中心的酶在许多催化过程中起到重要作用，例如常见的超氧化物歧化酶、光催化系统（PhotosystemII）中的析氧酶和核糖核苷酸还原酶等ADDINEN.CITE<EndNote><Cite><Author>Pecoraro</Author><Year>1994</Year><RecNum>371</RecNum><DisplayText><styleface="superscript">33</style></DisplayText><record><rec-number>371</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621146538">371</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Pecoraro,VincentL</author><author>Baldwin,MichaelJ</author><author>Gelasco,Andrew%JChemicalReviews</author></authors></contributors><titles><title>Interactionofmanganesewithdioxygenanditsreducedderivatives</title></titles><pages>807-826</pages><volume>94</volume><number>3</number><dates><year>1994</year></dates><isbn>0009-2665</isbn><urls></urls></record></Cite></EndNote>33。在1970年左右人们对过渡金属锰酶的氧气活化过程就开始进行了研究，1978年Taylor等人ADDINEN.CITE<EndNote><Cite><Author>Coleman</Author><Year>1978</Year><RecNum>372</RecNum><DisplayText><styleface="superscript">34</style></DisplayText><record><rec-number>372</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621146672">372</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Coleman,WM</author><author>Taylor,LT%JInorganicaChimicaActa</author></authors></contributors><titles><title>Reversibleμ-peroxocomplexesofmanganese(II)</title></titles><pages>L291-L293</pages><volume>30</volume><dates><year>1978</year></dates><isbn>0020-1693</isbn><urls></urls></record></Cite></EndNote>34发现二价锰配合物与氧气发生反应可以得到过氧根桥连的Mn(III)OOMn(III)双核锰配合物。但是接下来Armstrong等人ADDINEN.CITE<EndNote><Cite><Author>Kipke</Author><Year>2002</Year><RecNum>373</RecNum><DisplayText><styleface="superscript">35</style></DisplayText><record><rec-number>373</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621147007">373</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kipke,CaryA.</author><author>Scott,MichaelJ.</author><author>Gohdes,JoelW.</author><author>Armstrong,WilliamH.</author></authors></contributors><titles><title>Synthesis,structure,andmagneticpropertiesofareactivecomplexcontaininganearlylinearMnIII-O-MnIIIcore,bis[N,N-bis(5-nitrosalicylidene)-1,7-diamino-3-azapentanato(2-)]oxodimanganese</title><secondary-title>InorganicChemistry</secondary-title></titles><periodical><full-title>InorganicChemistry</full-title></periodical><pages>2193-2194</pages><volume>29</volume><number>12</number><section>2193</section><dates><year>2002</year></dates><isbn>0020-1669 1520-510X</isbn><urls></urls><electronic-resource-num>10.1021/ic00337a003</electronic-resource-num></record></Cite></EndNote>35的研究中发现二价锰活化氧气后得到的是以单个氧原子连接的Mn2III双核结构。事实上，早前对锰配合物活化氧气的研究中得到的锰氧中间体大多都是氧原子桥连的双核锰配合物。但是对具体的氧气活化反应机理尚不清晰，后来的研究发现过渡金属锰与氧气结合后形成MnO2中间体，再进一步发生OO键裂解得到高价的锰氧配合物。Nam等人ADDINEN.CITE<EndNote><Cite><Author>Hong</Author><Year>2016</Year><RecNum>72</RecNum><DisplayText><styleface="superscript">36</style></DisplayText><record><rec-number>72</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1605684230">72</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hong,S.</author><author>Lee,Y.M.</author><author>Sankaralingam,M.</author><author>Vardhaman,A.K.</author><author>Park,Y.J.</author><author>Cho,K.B.</author><author>Ogura,T.</author><author>Sarangi,R.</author><author>Fukuzumi,S.</author><author>Nam,W.</author></authors></contributors><auth-address>DepartmentofChemistryandNanoScience,EwhaWomansUniversity,Seoul03760,Korea. PicobiologyInstitute,GraduateSchoolofLifeScience,UniversityofHyogo,Hyogo678-1297,Japan. StanfordSynchrotronRadiationLightsource,SLACNationalAcceleratorLaboratory,MenloPark,California94025,UnitedStates.</auth-address><titles><title>AManganese(V)-OxoComplex:SynthesisbyDioxygenActivationandEnhancementofItsOxidizingPowerbyBindingScandiumIon</title><secondary-title>JAmChemSoc</secondary-title></titles><periodical><full-title>JAmChemSoc</full-title></periodical><pages>8523-32</pages><volume>138</volume><number>27</number><edition>2016/06/17</edition><keywords><keyword>ChemistryTechniques,Synthetic</keyword><keyword>ElectronTransport</keyword><keyword>Manganese/*chemistry</keyword><keyword>OrganometallicCompounds/*chemicalsynthesis/*chemistry</keyword><keyword>Oxygen/*chemistry</keyword></keywords><dates><year>2016</year><pub-dates><date>Jul13</date></pub-dates></dates><isbn>1520-5126(Electronic) 0002-7863(Linking)</isbn><accession-num>27310336</accession-num><urls><related-urls><url>/pubmed/27310336</url></related-urls></urls><electronic-resource-num>10.1021/jacs.6b03874</electronic-resource-num></record></Cite></EndNote>36报导称他们通过[MnIII(TAML)]活化氧气，在以烯烃作为底物的体系中成功得到高价锰氧产物[MnV(O)(TAML)]。他们提出的反应机理如图1-4所示：三价锰咔咯配合物活化氧气后得到锰超氧化物，然后通过路径b抓取底物烯烃的氢原子得到MnIVOOH物种，最终通过c过程发生OO键的裂解生成产物[MnV(O)(TAML)]。bcbc图1-4三价锰配合物催化活化氧气的反应机理过渡金属铜ADDINEN.CITEADDINEN.CITE.DATA37-39、钴ADDINEN.CITEADDINEN.CITE.DATA40,41和镍ADDINEN.CITE<EndNote><Cite><Author>Kieber-Emmons</Author><Year>2007</Year><RecNum>376</RecNum><DisplayText><styleface="superscript">42</style></DisplayText><record><rec-number>376</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621149088">376</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kieber-Emmons,M.T.</author><author>Riordan,C.G.</author></authors></contributors><auth-address>DepartmentofChemistryandBiochemistry,UniversityofDelaware,Newark,Delaware19716,USA.</auth-address><titles><title>Dioxygenactivationatmonovalentnickel</title><secondary-title>AccChemRes</secondary-title></titles><periodical><full-title>AccChemRes</full-title></periodical><pages>618-25</pages><volume>40</volume><number>7</number><edition>2007/05/24</edition><keywords><keyword>BindingSites</keyword><keyword>Catalysis</keyword><keyword>Cations,Monovalent/chemistry</keyword><keyword>Ligands</keyword><keyword>Models,Molecular</keyword><keyword>MolecularConformation</keyword><keyword>Nickel/*chemistry</keyword><keyword>Oxygen/*chemistry</keyword></keywords><dates><year>2007</year><pub-dates><date>Jul</date></pub-dates></dates><isbn>0001-4842(Print) 0001-4842(Linking)</isbn><accession-num>17518438</accession-num><urls><related-urls><url>/pubmed/17518438</url></related-urls></urls><electronic-resource-num>10.1021/ar700043n</electronic-resource-num></record></Cite></EndNote>42配合物也可以活化分子氧，氧气与金属中心结合后可以得到多种多样的Mn-O2（M=Cu、Co、Ni，n=1、2）金属氧物种（图1-5）。通过对不同的过渡金属配合物的研究，不仅可以为探究金属酶反应过程提供更多的数据支持，还可以对合成高性能催化剂提供理论指导。自从Karlin等人ADDINEN.CITE<EndNote><Cite><Author>Jacobson</Author><Year>2002</Year><RecNum>377</RecNum><DisplayText><styleface="superscript">43</style></DisplayText><record><rec-number>377</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621149721">377</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jacobson,RichardR.</author><author>Tyeklar,Zoltan</author><author>Farooq,Amjad</author><author>Karlin,KennethD.</author><author>Liu,Shuncheng</author><author>Zubieta,Jon</author></authors></contributors><titles><title>Acopper-oxygen(Cu2-O2)complex.Crystalstructureandcharacterizationofareversibledioxygenbindingsystem</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>3690-3692</pages><volume>110</volume><number>11</number><section>3690</section><dates><year>2002</year></dates><isbn>0002-7863 1520-5126</isbn><urls></urls><electronic-resource-num>10.1021/ja00219a071</electronic-resource-num></record></Cite></EndNote>43在1988年表征得到顺式，peroxo双核铜氧配合物以来，不同类型的铜氧配合物不断被成功合成出来。图1-5过渡金属氧配合物的几种不同构型（M=Cu，Co，Ni&n=1，2）Kitajima等人ADDINEN.CITE<EndNote><Cite><Author>Kitajima</Author><Year>2002</Year><RecNum>378</RecNum><DisplayText><styleface="superscript">44</style></DisplayText><record><rec-number>378</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621149994">378</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kitajima,Nobumasa</author><author>Fujisawa,Kiyoshi</author><author>Morooka,Yoshihiko</author><author>Toriumi,Koshiro</author></authors></contributors><titles><title>.mu.-.eta.2:.eta.2-Peroxobinuclearcoppercomplex,[Cu(HB(3,5-(Me2CH)2pz)3)]2(O2)</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>8975-8976</pages><volume>111</volume><number>24</number><section>8975</section><dates><year>2002</year></dates><isbn>0002-7863 1520-5126</isbn><urls></urls><electronic-resource-num>10.1021/ja00206a062</electronic-resource-num></record></Cite></EndNote>44在1989年合成了具有-peroxo配位构型的双核铜氧配合物（图1-4，e）的氧气转运蛋白（血蓝蛋白）和酪氨酸酶。从这以后许多不同配体的-peroxo双铜配合物不断地被合成出来。Tolman等人ADDINEN.CITE<EndNote><Cite><Author>Tolman</Author><Year>1997</Year><RecNum>379</RecNum><DisplayText><styleface="superscript">45</style></DisplayText><record><rec-number>379</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621150159">379</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tolman,WilliamB.</author></authors></contributors><titles><title>MakingandBreakingtheDioxygenO−OBond: NewInsightsfromStudiesofSyntheticCopperComplexes</title><secondary-title>AccountsofChemicalResearch</secondary-title></titles><periodical><full-title>AccountsofChemicalResearch</full-title></periodical><pages>227-237</pages><volume>30</volume><number>6</number><section>227</section><dates><year>1997</year></dates><isbn>0001-4842 1520-4898</isbn><urls></urls><electronic-resource-num>10.1021/ar960052m</electronic-resource-num></record></Cite></EndNote>45发现可以通过OO键之间的断裂和形成从而发生-peroxo配位构型的双核铜氧配合物与bis(oxo)双核铜氧配合物（图1-4，f）之间的互相转变，在二者的转变过程中涉及到两电子的氧化还原过程。另外，-peroxo双核铜氧配合物和bis(oxo)双核铜氧配合物之间的相对稳定性取决于空间位阻效应、电子效应、溶剂效应、抗衡离子和体系温度等。Hikichi等人ADDINEN.CITE<EndNote><Cite><Author>Hikichi</Author><Year>1998</Year><RecNum>380</RecNum><DisplayText><styleface="superscript">46</style></DisplayText><record><rec-number>380</rec-number><foreign-keys><keyapp="EN"db-id="tvx5ex5ebxevwlet2zjpt90rrvr2v2veeppx"timestamp="1621150457">380</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hikichi,Shiro</author><author>Yoshizawa,Michito</author><author>Sasakura,Yasuyuki</author><author>Akita,Munetaka</author><author>Moro-oka,Yoshihiko</author></authors></contributors><titles><title>FirstSynthesisandStructuralCharacterizationofDinuclearM(III)Bis(μ-oxo)ComplexesofNickelandCobaltwithHydrotris(pyrazolyl)borateLigand†</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>10567-10568</pages><volume>120</volume><number>40</number><section>10567</section><dates><year>1998</year></dates><isbn>0002-7863 1520-5126</isbn><urls></urls><electronic-resource-num>10.1021/ja981837l</electronic-resource-num></record></Cite></EndNote>46后来发现在类似配体体系下，过渡金属Ni和Co也可以得到bis(oxo)双核过渡金属氧配合物。虽然过渡金属配合物活化氧气的研究已经发展了六十余年，期间对Fe、Cu、