[Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(tetrahydrofuran)2] | 1186528-26-6

• 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: [Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(tetrahydrofuran)2]
• 英文别名: [Mo₂(H)₂{HC(N-2,6-iPr₂C₆H₃)₂}₂(tetrahydrofuran)₂]；[Mo₂(H)₂{HC(N-2,6-iPr₂C₆H₃)₂}₂(thf)₂]；[Mo₂{HC(N-2,6-ⁱPr₂C₆H₃)₂}₂]；Mo2{μ-k²-HC(N-2,6-iPr2C6H3)2}2；Mo2[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2
• CAS: 1186528-26-6
• 化学式: C₅₀H₇₀Mo₂N₄
• 分子量: 919.013
• InChiKey: GLNIYRXMWYGWDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  苯甲酰溴 、 [Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(tetrahydrofuran)2] 以 乙醚 为溶剂， 反应 0.17h， 以56%的产率得到anti-Mo₂(Br)(μ-κ²-OCC₆H₅)[μ-κ²-HC(N-2,6-ⁱPr₂C₆H₃)₂]₂
  参考文献：
  名称：

  酰基卤与五重键合的二钼Reaction酰胺反应还原成羧基的烷基炔烃配合物。

  摘要：

  Mediated by Lewis acids, a Friedel Crafts type of addition of acyl chlorides to allcynes gives beta-chloro alpha,beta-unsaturated ketones, which are important precursors to the preparation of heterocycles. A similar principle had been applied to the quintuply bonded dimolybdenum amidinate [Mo-2(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (1). Addition of acyl halides to 1 resulted in the formation of the beta-halo alpha,beta-quadruply bonded dimolybdenum acyl complexes anti-Mo-2(X)(mu-kappa(2)-OCR)[mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2) (R = Me, X = Cl (3); R = C6H5, X = Cl (4), Br (5); R = 4-FC6H4, X = Cl (6); R = 2-MeC6H4, X = Cl (7)). DFT calculations on Mo-2(C1)(mu-kappa(2)-OCMe)[mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] suggested that it equilibrates with the oxo alkylidyne Mo-2(O)(mu-Cl)(mu-CMe)[mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] in a ratio of about 100:1. The nucleophilic Mo=O functionality turned out to be reactive toward various electrophiles. Complexes 3-7 were subsequently treated with acyl halides RC(0)X to undergo haloacylation and yield carbyne-bridged dimolybdenum species [Mo-2(X)(mu-X)(mu-CR)(kappa(2)-O2CR)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (R = Me, X = Cl (10); R = C6H5, X = Cl (11), Br (12); R = 4-FC6H4, X = Cl (13); R = 2-MeC6H4, X = Cl (14)). However, when 1 was treated with the less reactive benzoyl fluoride, the two products [Mo-2(F)(mu-F)(mu-CC6H5)(kappa(2)-O2CC6H5)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (15) and [Mo-2(mu-eta(2)-1,2 eta(2)-4,5-C6H5COF)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (16) were isolated and the latter predominated. The oxo alkylidyne intermediates were further corroborated by reacting 4 with N-methylbenzimidoyl chloride and diphenylphosphinic chloride to give the two benzylidyne species [Mo-2(Cl)(mu-Cl)(mu-CC6H5)(kappa(2)-ONCH3C6H5)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (17) and [Mo-2(Cl)(mu-Cl)(mu-CC6H5)(kappa(2)-O2PPh2)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (18).Additionally, by swapping the addition order of benzoyl chloride and o-toluoyl chloride, we isolated the pair of benzylidyne isomers [Mo-2(Cl)(mu-Cl)(mu-CC6H5)(kappa(2)-O2C-2-MeC6H4)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (19) and [Mo-2(Cl)(mu-Cl)(mu-C-2-MeC6H4)(kappa(2)-O2CPh)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (20). All of these results revealed that the alkylidyne groups were derived from the first equivalent of the acyl group and the second acyl group served as an oxygen acceptor to give the carboxylato group. Interestingly, the Mo-C(alkylidyne) bond lengths did not change as the valency of Mo atoms decreased from IV to III, exemplified by KC8 reduction of 13 to give the halo-free alkylidyne complex [Mo-2(mu-C-4-FC6H4)(kappa(2)-O2C-4-FC6H4)(mu-kappa(2)-HC(N-2,6-(Pr2C6H3)-Pr-i)(2))(2)] (23).

  DOI：

  10.1021/acs.organomet.6b00132
• 作为产物：
  描述：

  [Mo₂(H)₂(μ-HC(N2,6-i-Pr₂C₆H₃)₂)₂(thf)₂] 以 环己烷 为溶剂， 反应 24.0h， 以75%的产率得到[Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(tetrahydrofuran)2]
  参考文献：
  名称：

  四氢键和五键键合钼配合物通过还原消除和氧化加成氢相互转化

  摘要：

  五加H 2产生四个：用[[H）MoMo（H）]核对双（ami基）络合物进行紫外线照射，诱导H 2的还原消除，并形成已知的五重键合MoMo物种（请参阅示意图） ）与H 2发生反应以还原[（H）MoMo（H）]。苯和甲苯中双（氢化物）物种的紫外线辐射产生芳烃配合物，其中芳烃桥接钼原子。浸渍= 2,6-二异丙基苯基。

  DOI：

  10.1002/anie.201209064

文献信息

• Experimental and Theoretical Studies on Arene-Bridged Metal-Metal-Bonded Dimolybdenum Complexes
  作者：Mario Carrasco、Natalia Curado、Eleuterio Álvarez、Celia Maya、Riccardo Peloso、Manuel L. Poveda、Amor Rodríguez、Eliseo Ruiz、Santiago Álvarez、Ernesto Carmona

  DOI：10.1002/chem.201400236

  日期：2014.5.12

  The bis(hydride) dimolybdenum complex, [Mo2(H)2HC(N‐2,6‐iPr2C6H3)2}2(thf)2], 2, which possesses a quadruply bonded Mo2II core, undergoes light‐induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the MoI2 complexes [Mo2HC(N‐2,6‐iPr2C6H3)2}2(arene)], 3⋅C6H6 and 3⋅C6H5Me, respectively. The analogous C6H5OMe, p‐C6H4Me2, C6H5F, and p‐C6H4F2

  双（氢化物）dimolybdenum络合物，[沫2（H）2 HC（Ñ -2,6-我镨2 ç 6 ħ 3）2 } 2（THF）2 ]，2，其具有一个四重粘合的Mo 2 II核经过光诱导（365 nm）还原性消除H 2和苯和甲苯溶液中的芳烃配位，形成Mo I 2络合物[Mo 2 HC（N− 2,6‐ i Pr 2 C 6高3）2 } 2（芳烃）]，3⋅C 6 ħ 6和3⋅C 6 ħ 5我，分别。还通过热或光化学方法制备了类似的C 6 H 5 OMe，p C 6 H 4 Me 2，C 6 H 5 F和p C 6 H 4 F 2衍生物，但是使用了不同的Mo 2复杂的前体。X射线晶体学和NMR溶液研究表明，芳烃的分子桥接Mo的钼原子我2芯，协调向每个在一个η 2方式。在溶液中，芳烃在NMR时标上绕Mo 2-芳烃轴快速旋转。对于取代的芳烃，NMR数据与主要旋转异构体的存在是一致的，在旋转异构体中，金属原子与更富电子的CC键配位。
• Journey from Mo−Mo Quadruple Bonds to Quintuple Bonds
  作者：Yi-Chou Tsai、Hong-Zhang Chen、Chie-Chieh Chang、Jen-Shiang K. Yu、Gene-Hsiang Lee、Yu Wang、Ting-Shen Kuo

  DOI：10.1021/ja905035f

  日期：2009.9.9

  Heating K(4)Mo(2)Cl(8) and 2 equiv of Li[RC(NDipp)(2)] (R = H, Ph; Dipp = 2,6-i-Pr(2)C(6)H(3)) in tetrahydrofuran (THF) at 60 degrees C gives two paddlewheel type quadruply bonded dimolybdenum complexes, Mo(2)(mu-Cl)[Cl(2)Li(OEt(2))][mu-eta(2)-RC(N-2,6-i-Pr(2)C(6)H(3))(2)](2) (R = H (1), Ph (2)). The Mo-Mo bond lengths of 1 and 2 are 2.0875(4) and 2.0756(8) A, respectively, indicating typical Mo-Mo

  加热 K(4)Mo(2)Cl(8) 和 2 当量的 Li[RC(NDipp)(2)] (R = H, Ph; Dipp = 2,6-i-Pr(2)C(6) H(3)) 在四氢呋喃 (THF) 中在 60 摄氏度下得到两个桨轮型四键二钼配合物，Mo(2)(mu-Cl)[Cl(2)Li(OEt(2))][mu-eta( 2)-RC(N-2,6-i-Pr(2)C(6)H(3))(2)](2) (R = H (1), Ph (2))。1 和 2 的 Mo-Mo 键长分别为 2.0875(4) 和 2.0756(8) A，表明是典型的 Mo-Mo 四键。两个电子对 1 和 2 的还原导致其相应的 Mo-Mo 五重键复合物 Mo(2)[mu-eta(2)-RC(N-2,6-i-Pr(2)C( 6)H(3))(2)](2) (R = H (3), Ph (4))，Mo-Mo 键长急剧下降到 2.0187(9)
• Reactions of Metal-Metal Quintuple Bonds with Alkynes: [2+2+2] and [2+2] Cycloadditions
  作者：Hong-Zhang Chen、Shih-Cheng Liu、Chun-Hsu Yen、Jen-Shiang K. Yu、Yun-Jen Shieh、Ting-Shen Kuo、Yi-Chou Tsai

  DOI：10.1002/anie.201205027

  日期：2012.10.8

  amidinate 1 reacts with two equivalents of 1‐pentyne through a [2+2+2] cycloaddition reaction to give the first examples of the benzannulated product 2. The C4Mo2 rings exhibit aromatic character. Treatment of 1 with internal alkynes afforded the 2:1 and 1:1 [2+2] cycloadducts, which are mechanistically associated with the formation of 2.

  举手击掌！五重键合的a基钼1通过[2 + 2 + 2]环加成反应与两当量的1-戊炔反应，生成苯甲环化产物2的第一个实例。C 4 Mo 2环表现出芳香性。用内部炔烃处理1得到2：1和1：1 [2 + 2]环加合物，从机理上讲与2的形成有关。
• The MoMo Quintuple Bond as a Ligand to Stabilize Transition-Metal Complexes
  作者：Duan-Yen Lu、Peter P.-Y. Chen、Ting-Shen Kuo、Yi-Chou Tsai

  DOI：10.1002/anie.201504414

  日期：2015.7.27

  employment of the MoMo quintuple bonded amidinate complex to stabilize Group 10 metal fragments (Et3P)2M} (M=Pd, Pt) and give rise to the isolation of the unprecedented δ complexes. X‐ray analysis unambiguously revealed short contacts between Pd or Pt and two Mo atoms and a slight elongation of the MoMo quintuple bond in these two compounds. Computational studies show donation of the MoMo quintuple‐bond

  本文中，我们报道了使用MOMO五元键合的mid基络合物来稳定第10组金属碎片（Et 3 P）2 M}（M = Pd，Pt）并导致前所未有的δ络合物的分离。X射线分析清楚地表明，这两种化合物中Pd或Pt与两个MO原子之间的短接触以及MOMO五元键的轻微延伸。计算研究表明，将MOMO五重键δ电子捐赠给Pd或Pt上的空σ轨道，并将填充的Pd或Pt dππ轨道的背捐赠给MOMOδ *能级（LUMO），这是一致的使用Dewar–Chatt–Duncanson模型。