查看“︁有机钼化学”︁的源代码

'''有機鉬化學'''，是一門專門研究包含碳-鉬鍵的化合物（'''有機鉬化合物'''）的化學的學科，是[[有机金属化学|有機金屬化學]]的分支。[[钼|鉬]]、[[钨|鎢]]這些較重的[[6族元素]]會生成與[[有機鉻化學|有機鉻化合物]]相似的有機金屬化合物，但通常鉬與鎢會有更高的[[氧化数|氧化數]]。<ref>{{Cite journal |author=Poli, R. |year=2008 |title=High oxidation state organomolybdenum and organotungsten chemistry in protic environments |url=https://hal.archives-ouvertes.fr/hal-03192719/file/244-10.1016-j.ccr.2007.11.029-Accepted.pdf |journal=Coord. Chem. Rev. |volume=252 |issue=15–17 |pages=1592–1612 |doi=10.1016/j.ccr.2007.11.029 |access-date=2022-08-29 |archive-date=2022-02-06 |archive-url=https://web.archive.org/web/20220206174205/https://hal.archives-ouvertes.fr/hal-03192719/file/244-10.1016-j.ccr.2007.11.029-Accepted.pdf |dead-url=no }}</ref>

== Mo(0)或更低價態的化合物 ==
於[[六羰基钼|六羰基鉬]]中，鉬是零價的，是很多衍生物的前體。它可以跟[[有机锂试剂|有機鋰試劑]]反應，生成酰基陰離子(anionic acyls)。此陰離子可以發生O-[[烷基化|烷基化反應]]，生成[[Fischer卡宾|Fischer卡賓]]。此外，六羰基鉬可以跟[[芳香烃|芳烴]]反應，生成具有鋼琴凳（piano stool）幾何構型的配合物，例如[[均三甲苯三羰基钼|均三甲苯三羰基鉬]]。[[環庚三烯三羰基鉬]]可以跟[[三苯甲烷]]的鹽反應，生成環庚三烯基配合物。<ref>{{cite journal |author=[[Malcolm Green (chemist)|Green M. L. H.]], Ng D. K. P. |year=1995 |title=Cycloheptatriene and -enyl Complexes of the Early Transition Metals |journal=Chemical Reviews |volume=95 |issue=2 |pages=439–73 |doi=10.1021/cr00034a006}}</ref>反應式如下：
[[File:(Mesitylene)molybdenum_tricarbonyl.png|thumb|172x172px|均三甲苯三羰基鉬的結構]]
<chem>(C7H8)Mo(CO)3 + (C6H5)3C+ -> [(C7H7)Mo(CO)3]+ + (C6H5)3CH</chem>
[[File:CHTMo(CO)3.png|thumb|144x144px|環庚三烯三羰基鉬的結構]]
六羰基鉬可被[[氧化还原反应|還原]]，生成 [Mo(CO)<sub>5</sub>]<sup>2−</sup>，其中鉬為負二價。<ref>{{Cite journal |author=Ellis, J. E. |year=2003 |title=Metal Carbonyl Anions: from [Fe(CO)<sub>4</sub>]<sup>2−</sup> to [Hf(CO)<sub>6</sub>]<sup>2−</sup> and Beyond |journal=[[Organometallics]] |volume=22 |issue=17 |pages=3322–3338 |doi=10.1021/om030105l}}</ref>
不含CO的零價鉬化合物比[[金屬羰基配合物|羰基化合物]]更具還原性，在動力學上亦更不穩定。<ref>{{cite encyclopedia|author=Flower, K. R.|title=Molybdenum Compounds without CO or Isonitrile Ligands|editor1=[[Michael Mingos|Mingos, D. Michael P.]]|editor2=[[Robert H. Crabtree|Crabtree, Robert H.]]|encyclopedia=Comprehensive Organometallic Chemistry III|year=2007|volume=5|pages=513–595|doi=10.1016/B0-08-045047-4/00072-8|isbn=9780080450476}}</ref>

== Mo(II)的化合物 ==
[[六羰基钼|六羰基鉬]]的鹵化可製備鉬羰基鹵化物，它也可以用來製備其他化合物。<ref>Joseph L. Templeton "Four-Electron Alkyne Ligands in Molybdenum(II) and Tungsten(II) Complexes" Advances in Organometallic Chemistry 1989, Volume 29, Pages 1–100.{{doi|10.1016/S0065-3055(08)60352-4}}</ref>同時，六羰基鉬和[[乙酸]]反應可以得到[[乙酸钼(II)|乙酸鉬(II)]]，反應中[[金屬羰基配合物|羰基]]被[[乙酸盐|乙酸根]]取代，放出[[一氧化碳]]，鉬從零價氧化至正二價。<ref name="brignole">{{cite journal |last1=Brignole |first1=Alicia B. |last2=Cotton |first2=F. A. |last3=Dori |first3=Z. |last4=Dori |first4=Z. |last5=Dori |first5=Z. |last6=Wilkinson |first6=G. |year=2007 |title=Rhenium and Molybdenum Compounds Containing Quadruple Bonds |pages=81–89 |doi=10.1002/9780470132449.ch15 |issn=19344716}}</ref><ref name="pence">{{cite journal |last1=Pence |first1=Laura E. |last2=Weisgerber |first2=Amy M. |last3=Maounis |first3=Florence A. |year=1999 |title=Synthesis of Molybdenum-Molybdenum Quadruple Bonds: A Multistep Advanced Synthesis Laboratory Experiment |url=https://archive.org/details/sim_journal-of-chemical-education_1999-03_76_3/page/404 |journal=Journal of Chemical Education |volume=76 |issue=3 |pages=404 |doi=10.1021/ed076p404 |issn=0021-9584}}</ref>反應式如下：

<chem>2 Mo(CO)6 + 4 HO2CCH3 -> Mo2(O2CCH3)4 + 12 CO + 2 H2</chem>

[[乙酸钼(II)|乙酸鉬(II)]]跟[[甲基锂|甲基鋰]]反應可生成<chem>Li4[Mo2(CH3)8]</chem>。

== Mo(IV)的化合物 ==
[[二氯二茂鉬|二氯化二茂鉬]]、[[二氢化二茂钼|二氫化二茂鉬]]等化合物中，鉬是四價。

== Mo(V)、Mo(VI)的化合物 ==
<chem>Mo(CH3)5</chem>、<chem>Mo(CH3)6</chem>以及<chem>[Mo(CH3)7]^-</chem>是已知的物種。<ref>{{cite encyclopedia|author=Flower, K. R.|title=Molybdenum Compounds without CO or Isonitrile Ligands|editor1=[[Michael Mingos|Mingos, D. Michael P.]] |editor2=[[Robert H. Crabtree|Crabtree, Robert H.]] |encyclopedia=Comprehensive Organometallic Chemistry III|year=2007|volume=5|pages=513–595|doi=10.1016/B0-08-045047-4/00072-8|isbn=9780080450476}}</ref>

用於[[烯烴複分解反應]]的[[施罗克催化剂|施羅克催化劑]]内含Mo(VI)。<ref>{{cite journal | author = R.R. Schrock | title = High-oxidation-state molybdenum and tungsten alkylidene complexes | year = 1986 | journal = [[Acc. Chem. Res.]] | doi = 10.1021/ar00131a003 | volume = 19 | issue = 11 | pages = 342–348}}</ref>然而，用施羅克標準的方法來製備這些催化劑是有問題的。下圖的物種17在室溫下是活潑的。<ref>{{cite journal |last1=Tsai |first1=Yi-Chou |last2=Cummins |first2=Christopher C. |year=2000 |title=Facile Synthesis of Trialkoxymolybdenum(VI) Alkylidyne Complexes for Alkyne Metathesis |url=https://pubs.acs.org/doi/abs/10.1021/om000644f |journal=Organometallics |volume=19 |issue=25 |page=5260 |doi=10.1021/om000644f |access-date=2022-08-30 |archive-date=2022-02-06 |archive-url=https://web.archive.org/web/20220206202336/https://pubs.acs.org/doi/abs/10.1021/om000644f |dead-url=no }}</ref>
[[File:Cummins_first_Mo_example.png|center|750x750px]]
原本設計用來計量[[固氮作用|裂解氮]]的相關前體18有更多用途。<ref>{{cite journal |last1=Cummins |first1=Christopher C. |year=1998 |title=Reductive cleavage and related reactions leading to molybdenum–element multiple bonds: new pathways offered by three-coordinate molybdenum(III) |url=https://pubs.rsc.org/en/content/articlelanding/1998/CC/a802402b |journal=Chemical Communications |issue=17 |pages=1777–1786 |doi=10.1039/A802402B |access-date=2022-08-30 |archive-date=2022-06-20 |archive-url=https://web.archive.org/web/20220620232145/https://pubs.rsc.org/en/content/articlelanding/1998/CC/a802402b |dead-url=no }}</ref><ref>{{cite journal |last1=Fürstner |first1=Alois |year=1999 |title=Mo[N(t-Bu)(Ar)]3 Complexes As Catalyst Precursors: In Situ Activation and Application to Metathesis Reactions of Alkynes and Diynes |url=https://pubs.acs.org/doi/10.1021/ja991340r |journal=J. Am. Chem. Soc. |volume=121 |issue=40 |page=9453 |doi=10.1021/ja991340r |access-date=2022-08-30 |archive-date=2022-09-26 |archive-url=https://web.archive.org/web/20220926075440/https://pubs.acs.org/doi/10.1021/ja991340r |dead-url=no }}</ref>實際上，當配合物18與[[二氯甲烷]]在[[甲苯]]中作用，主要生成配合物19與20。<ref>{{cite journal |last1=Agapie |first1=Theodor |year=2002 |title=Methine (CH) Transfer via a Chlorine Atom Abstraction/Benzene-Elimination Strategy: Molybdenum Methylidyne Synthesis and Elaboration to a Phosphaisocyanide Complex |url=https://pubs.acs.org/doi/10.1021/ja017278r |journal=J. Am. Chem. Soc. |volume=124 |issue=11 |pages=2412–2413 |doi=10.1021/ja017278r |pmid=11890770 |access-date=2022-08-30 |archive-date=2022-02-06 |archive-url=https://web.archive.org/web/20220206202336/https://pubs.acs.org/doi/10.1021/ja017278r |dead-url=no }}</ref>而當配合物18跟[[1,1-二氯乙烷]]反應，[[胺]]等極性基團可被運用，而這些基團是可以鈍化具有[[酸碱电子理论|路易斯酸性]]的配合物，如 Schrock 配合物。基於這發現，Moore 和其他人嘗試以其他偕二氯烷烴作活化劑，以延長這些催化劑的壽命。<ref>{{cite journal |last1=Zhang |first1=Wei |last2=Moore |first2=Jeffrey |year=2004 |title=Highly Active Trialkoxymolybdenum(VI) Alkylidyne Catalysts Synthesized by a Reductive Recycle Strategy |url=https://pubs.acs.org/doi/10.1021/ja0379868 |journal=J. Am. Chem. Soc. |volume=126 |issue=1 |pages=329–335 |doi=10.1021/ja0379868 |pmid=14709099 |access-date=2022-08-30 |archive-date=2022-09-24 |archive-url=https://web.archive.org/web/20220924140559/https://pubs.acs.org/doi/10.1021/ja0379868 |dead-url=no }}</ref>加入[[鎂]]金屬可以將副產物氯化物重新轉化為反應物。同時，以[[对硝基苯酚|對硝基苯酚]]等缺電子的[[配體]]取代原先配體，可以得到一個非常活潑的催化劑22。它在很多範疇都非常有效，尤其是在[[高分子化学|聚合物化學]]與[[材料科学|材料科學]]兩個領域。<ref>{{cite journal |last1=Zhang |first1=Wei |last2=Moore |first2=Jeffrey |year=2004 |title=Synthesis of Poly(2,5-thienyleneethynylene)s by Alkyne Metathesis |url=https://pubs.acs.org/doi/10.1021/ma049371g |journal=Macromolecules |volume=37 |issue=11 |page=3973 |bibcode=2004MaMol..37.3973Z |doi=10.1021/ma049371g |access-date=2022-08-30 |archive-date=2022-02-06 |archive-url=https://web.archive.org/web/20220206202355/https://pubs.acs.org/doi/10.1021/ma049371g |dead-url=no }}</ref>此外，以[[三齒配體]]醇解配合物21，可延長化合物的壽命，亦可擴濶可用受體的範圍。<ref>{{cite journal |last1=Zhang |first1=Wei |year=2011 |title=Introducing A Podand Motif to Alkyne Metathesis Catalyst Design: A Highly Active Multidentate Molybdenum(VI) Catalyst that Resists Alkyne Polymerization |url=https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201007559 |journal=Angew. Chem. Int. Ed. |volume=50 |issue=15 |pages=3435–3438 |doi=10.1002/anie.201007559 |pmid=21394862 |access-date=2022-08-30 |archive-date=2022-02-06 |archive-url=https://web.archive.org/web/20220206205308/https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201007559 |dead-url=no }}</ref>

但即使配合物18有很多好處，它其實不僅對氧化與水解敏感，而且非常活潑，連氮氣分子都可以裂解，因此要小心使用。
[[File:Mo(III)_complex.png|center|800x800px]]

== 應用 ==
有機鉬化合物是可用作[[烯烃复分解反应|烯烴複分解]]<ref name="RRS">{{cite journal |author=R.R. Schrock |year=1986 |title=High-oxidation-state molybdenum and tungsten alkylidene complexes |journal=[[Acc. Chem. Res.]] |volume=19 |issue=11 |pages=342–348 |doi=10.1021/ar00131a003}}</ref>、[[炔烴複分解]]反應<ref>{{cite journal |author=Wei Zhang |author2=Yunyi Lu |author3=Jeffrey S. Moore |year=2007 |title=Preparation of a Trisamidomolybdenum(VI) Propylidyne Complex |journal=Org. Synth. |volume=84 |page=163 |doi=10.15227/orgsyn.084.0163}}{{cite journal |author=Wei Zhang |author2=Hyeon Mo Cho |author3=Jeffrey S. Moore |year=2007 |title=Preparation of a Carbazole-Based Macrocycle via Precipitation-driven Alkyne Metathesis |url=https://pdfs.semanticscholar.org/ca4c/e67498098e992260c59bb2233d1870d02a71.pdf |url-status=dead |journal=Org. Synth. |volume=84 |page=177 |doi=10.15227/orgsyn.084.0177 |s2cid=93992722 |archive-url=https://web.archive.org/web/20200219161527/https://pdfs.semanticscholar.org/ca4c/e67498098e992260c59bb2233d1870d02a71.pdf |archive-date=2020-02-19}}</ref>的催化劑。
[[File:SchrockMetathesisCatalysts.png|center|500x500px|Some commercially available Schrock catalysts.]]
在[[考夫曼烯化反应|考夫曼烯化反應]]中，[[三氯化钼|三氯化鉬]]與[[甲基锂|甲基鋰]]反應生成一個配合物，將[[醛]]、[[酮]]轉變為[[亚甲基|亞甲基]][[烯烃|烯烴]]。<ref>{{cite journal |author=Kauffmann, T. |year=1997 |title=Organomolybdenum and organotungsten reagents. 7. Novel reactions of organomolybdenum and organotungsten compounds: additive-reductive carbonyl dimerization, spontaneous transformation of methyl ligands into μ-methylene ligands, and selective carbonylmethylenation |journal=Angew. Chem. Int. Ed. Engl. |volume=36 |pages=1259–1275 |doi=10.1002/anie.199712581}}</ref>
[[File:Kauffmann_mechanismus.png|center|500x500px]]

== 參考資料 ==
{{reflist}}

== 參見 ==
{{含碳化合物}}

[[category:有机鉬化合物]]
[[category:有機金屬化學]]