Mo(IV)Cl(N(t-Bu)(3,5-C6H3Me2))3 | 251306-52-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Mo(IV)Cl(N(t-Bu)(3,5-C6H3Me2))3
• 英文别名: MoCl(N(tert-Bu)C6H3(CH3)2)3；[MoCl(Me3CN(3,5-C6H3Me2))3]；[MoCl(N(tBu)C6H3Me2)3]
• CAS: 251306-52-2
• 化学式: C₃₆H₅₄ClMoN₃
• 分子量: 660.238
• InChiKey: JYVNDWLTVVCZOV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  41.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  9.72
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Mo(IV)Cl(N(t-Bu)(3,5-C6H3Me2))3 在 magnesium 、 NaH 作用下， 以 四氢呋喃 为溶剂， 生成 NMo(N[((t)Bu)(3,5-C6H3Me2)])3
  参考文献：
  名称：

  A Cycle for Organic Nitrile Synthesis via Dinitrogen Cleavage

  摘要：

  In the presence of NaH, the reaction between N2 and Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) proceeds at room temperature to afford NMo(N[t-Bu]Ar)3 (95%). Lewis acidic silyl triflates (Me3SiOTf + pyridine or (i-Pr)3SiOTf) mediate a reaction between acid chlorides and NMo(N[t-Bu]Ar)3 to yield acyl imidos [RC(O)NMo(N[t-Bu]Ar)3][OTf] (R = Me, 92%; Ph, 75%; t-Bu, 64%). The reduction of [RC(O)NMo(N[t-Bu]Ar)3][OTf] by magnesium anthracene followed by treatment with Me3SiOTf affords molybdenum ketimides, R(Me3SiO)CNMo(N[t-Bu]Ar)3 (R = Me, 82%; Ph, 77%; t-Bu, 46%). Exposing R(Me3SiO)CNMo(N[t-Bu]Ar)3 to SnCl2 or ZnCl2 produces ClMo(N[t-Bu]Ar)3 (71-93% for SnCl2) and RCN (97-99%). Magnesium metal reduces ClMo(N[t-Bu]Ar)3 to Mo(N[t-Bu]Ar)3 (74%), completing a synthetic cycle. New strategies for the functionalization of sterically hindered nitrides and nitrile extrusion from d2 ketimides are presented in the context of a new route for derivatizing N2.

  DOI：

  10.1021/ja066090a
• 作为产物：
  描述：

  magnesium anthracene 以 乙醚 为溶剂， 生成 Mo(IV)Cl(N(t-Bu)(3,5-C6H3Me2))3
  参考文献：
  名称：

  A Cycle for Organic Nitrile Synthesis via Dinitrogen Cleavage

  摘要：

  In the presence of NaH, the reaction between N2 and Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) proceeds at room temperature to afford NMo(N[t-Bu]Ar)3 (95%). Lewis acidic silyl triflates (Me3SiOTf + pyridine or (i-Pr)3SiOTf) mediate a reaction between acid chlorides and NMo(N[t-Bu]Ar)3 to yield acyl imidos [RC(O)NMo(N[t-Bu]Ar)3][OTf] (R = Me, 92%; Ph, 75%; t-Bu, 64%). The reduction of [RC(O)NMo(N[t-Bu]Ar)3][OTf] by magnesium anthracene followed by treatment with Me3SiOTf affords molybdenum ketimides, R(Me3SiO)CNMo(N[t-Bu]Ar)3 (R = Me, 82%; Ph, 77%; t-Bu, 46%). Exposing R(Me3SiO)CNMo(N[t-Bu]Ar)3 to SnCl2 or ZnCl2 produces ClMo(N[t-Bu]Ar)3 (71-93% for SnCl2) and RCN (97-99%). Magnesium metal reduces ClMo(N[t-Bu]Ar)3 to Mo(N[t-Bu]Ar)3 (74%), completing a synthetic cycle. New strategies for the functionalization of sterically hindered nitrides and nitrile extrusion from d2 ketimides are presented in the context of a new route for derivatizing N2.

  DOI：

  10.1021/ja066090a
• 作为试剂：
  描述：

  1,6-bis(pent-3-yn-1-yl)hexanedioate 在 Mo(IV)Cl(N(t-Bu)(3,5-C6H3Me2))3 、 二溴甲烷 作用下， 以 甲苯 为溶剂， 以84%的产率得到1,8-dioxacyclotetradec-11-yne-2,7-dione
  参考文献：
  名称：

  Mo[N(t-Bu)(Ar)]₃ Complexes As Catalyst Precursors:  In Situ Activation and Application to Metathesis Reactions of Alkynes and Diynes

  摘要：

  DOI：

  10.1021/ja991340r

文献信息

• A reductive recycle strategy for the facile synthesis of molybdenum(VI) alkylidyne catalysts for alkyne metathesisElectronic supplementary information (ESI) available: spectral data. See http://www.rsc.org/suppdata/cc/b2/b212405j/
  作者：Wei Zhang、Stefan Kraft、Jeffrey S. Moore

  DOI：10.1039/b212405j

  日期：2003.3.24

  A convenient synthesis of trisamido molybdenum(VI) alkylidyne complexes has been developed, in which the key step is the addition of a geminal dichloride to a trisamido molybdenum(III) complex in the presence of magnesium to continuously recycle unwanted side product 4, selectively generating the desired alkylidyne complexes in high yield.

  已经开发出一种方便的合成三氨基钼(VI)烷基炔络合物的方法，其关键步骤是在镁的存在下将一氟二氯化物加到三氨基钼(III)络合物中，以持续回收不必要的副产物4，选择性地产生所需的烷基炔络合物，并获得高产率。
• Highly Active Trialkoxymolybdenum(VI) Alkylidyne Catalysts Synthesized by a Reductive Recycle Strategy
  作者：Wei Zhang、Stefan Kraft、Jeffrey S. Moore

  DOI：10.1021/ja0379868

  日期：2004.1.1

  A systematic study of alkyne metathesis catalyzed by trialkoxymolybdenum(VI) alkylidyne complexes is reported, in which substrate functional groups, alkynyl substituents, and catalyst ligands are varied. Sterically hindered trisamidomolybdenum(VI) propylidyne complex 5 was prepared conveniently through a previously communicated reductive recycle strategy. Alcoholysis of 5 with various phenols/alcohols

  报道了由三烷氧基钼 (VI) 烷炔配合物催化的炔复分解的系统研究，其中底物官能团、炔基取代基和催化剂配体各不相同。空间位阻三氨基钼 (VI) 丙炔配合物 5 通过先前传达的还原循环策略方便地制备。5与各种酚类/醇类的醇解为炔烃在室温下复分解提供了一套活性催化剂，其中以对硝基苯酚为配体的催化剂表现出最高的催化活性，并与多种官能团和溶剂相容。能够使用高活性钼 (VI) 催化剂的一个关键发现是用丁炔基取代起始炔底物上常用的丙炔基取代基。在使用 1,2,4-三氯苯作为不挥发性溶剂的减压下，丁炔基取代化合物的炔烃复分解在 30 摄氏度下进行得很好，提供了高产率 (83%-97%) 的二聚体。讨论了丁炔基底物所起特殊作用的合理化。
• Nitrogen fixation to cyanide at a molybdenum center
  作者：John J. Curley、Anthony F. Cozzolino、Christopher C. Cummins

  DOI：10.1039/c0dt01326a

  日期：——

  [MeOCH2NMo(N[tBu]Ar)3]+ as its triflate salt in 88% yield. Treatment of the latter with LiN(SiMe3)2 provided blue methoxyketimide complex MeO(H)CNMo(N[tBu]Ar)3 in 95% yield. Conversion of the latter to the terminal cyanide complex NCMo(N[tBu]Ar)3, which was the subject of a single-crystal X-ray diffraction study, was accomplished in 51% yield upon treatment with a combination of SnCl2 and Me2NSiMe3.

  N 2衍生的氮化物NMo（N [ t Bu] Ar）3的容易的甲氧基甲基化，以88％的收率提供亚胺阳离子[MeOCH 2 NMo（N [ t Bu] Ar）3 ] +作为其三氟甲磺酸盐。用LiN（SiMe 3）2处理后者，得到蓝色甲氧基酮亚胺络合物MeO（H）CNMo（N [ t Bu] Ar）3，产率为95％。将后者转化为末端氰化物络合物NCMo（N [ t Bu] Ar）3，这是单晶X射线衍射研究的主题，经SnCl 2和NaCl的组合处理，收率为51％。我2 NSiMe 3。