(η5-C5Me5)*Mo{N(iPr)C(Me)N(iPr)}(CO)2 | 1241890-64-1

• 英文名称: (η5-C5Me5)*Mo{N(iPr)C(Me)N(iPr)}(CO)2
• 英文别名: (η⁵-C₅Me₅)*Mo{N(iPr)C(Me)N(iPr)}(CO)₂；C_p*Mo[N(ⁱPr)C(Me)N(ⁱPr)](CO)₂；C_p*Mo[N(isopropyl)C(Me)N(isopropyl)](CO)₂；Cp*Mo{N(iPr)C(Me)N(iPr)}(CO)₂；(η5-C5Me5)Mo[N(iPr)CMeN(iPr)](CO)2；(η5-C5Me5)Mo[N(i-Pr)C(Me)N(i-Pr)](CO)2
• CAS: 1241890-64-1
• 化学式: C₂₀H₃₂MoN₂O₂
• 分子量: 428.426
• InChiKey: JPRANWSNOYFQKQ-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：

  norbornene 、 (η5-C5Me5)*Mo{N(iPr)C(Me)N(iPr)}(CO)2 以 苯 为溶剂， 生成 Cp*[N(ⁱPr)C(CH₃)N(ⁱPr)]Mo(CO)(C₇H₁₀)
  参考文献：
  名称：

  对于M = Mo，W和L = N2，NCMe，η2-，第6组配合物（η5-C5Me5）[N（iPr）C（Me）N（iPr）] M（CO）（L）中的小分子活化烯烃，SMe2，C3H6O

  摘要：

  A series of midvalent monocyclopentadienyl monoamidiriate (CPAM) group 6 complexes of the general formula Cp*[N(Pr-i)C(Me)N(Pr-i)]M(CO)(L) (II), where Cp* = eta(5)-C5Me5 and M = Mo, W, have been prepared, and most of them have been structurally characterized. Treatment of the ditungsten "end-on-bridged" dinitrogen complex {Cp* [N(Pr-i)C(Me)N(Pr-i)]W}(2) (mu-eta(1):eta(1)-N-2) (3) with excess NCMe under a CO atmosphere produced the ditungsten bridging diimido complex {Cp*[N(Pr-i)C(Me)N(Pr-i)]W}(2){mu-eta(1):eta(1)-NC(Me)=C(Me)N] (4). Photolysis of Cp*[N(Pr-i)C-(Me)N(Pr-i)]M(CO)(2), where M = Mo (6), W (7), or treatment of Cp*[N(Pr-i)C(Me)N(Pr-i)]Mo(CO)(NCMe) (1a) with excess alkene provided Cp*[N(Pr-i)C(Me)N(Pr-i)]-M(CO)(L) for M = Mo and L = eta(2)-ethene (8), M = W and L = eta(2)-ethene (9), M = Mo and L = eta(2)-norbomene (10), M = W and L = eta(2)-norbomene (11), M = W and L = eta(2)-cyclopentene (12), M = Mo and L = eta(2)-cyclopentene (13), and M = Mo and L = eta(2)-styrene (14). When isobutene was employed as the alkene, C-H bond activation occurred to produce Cp*[N(Pr-i)C(Me)-N(Pr-i)]W(H)(eta(3)-C4H7) (15). Photolysis of 7 in the presence of SMe2 provided Cp*[N(Pr-i)C(Me)N(Pr-i)]W[kappa-C,Omicron-C(O)Me](SMe) (16) through oxidative C-S bond activation of a coordinated SMe2, followed by 1,1-carbonyl migratory insertion into the new W-C bond. Finally, reaction of la with propylene oxide (C3H6O) provided the 16-electron complex Cp*[N(Pr-i)C(Me)N(Pr-i)]Mo[C(O)CH(Me)CH2O] (19) via similar oxidative C-O bond activation of coordinated C3H6O, followed by 1,1-carbonyl migratory insertion into the Mo-C bond of an intermediate metallaoxetane. Undera CO atmosphere, 19 is converted to the 18-electron complex Cp*[N(Pr-i)C(Me)N(Pr-i)]Mo[C(O)CH(Me)CH2O]CO) (20). These results provide additional support for the development of new stoichiometric and catalytic transformations that are mediated by CPAM group 6 metal complexes and that are relevant to the goal of small-molecule fixation.

  DOI：

  10.1021/acs.organomet.6b00131
• 作为产物：
  描述：

  一氧化碳 、 {Cp*Mo[N(iPr)C(Me)N(iPr)]}2(μ-η1:η1-N2) 以 甲苯 为溶剂， 以71%的产率得到(η5-C5Me5)*Mo{N(iPr)C(Me)N(iPr)}(CO)2
  参考文献：
  名称：

  第 6 组“End-On-Bridged”双核配合物中的二氮络合和 N≡N 活化程度，{(η5-C5Me5)M[N(i-Pr)C(Me)N(i-Pr)]}2 (μ-η1:η1-N2) (M = Mo 和 W)

  摘要：

  Cp*M[N(i-Pr)C(Me)N(i-Pr)]Cl(3) 的化学还原 (Cp* = eta(5)-C(5)Me(5)) (1, M = Mo) 和 (2, M = W) 在 THF 中使用 0.5% NaHg 提供了极好的抗磁性双核端桥双氮复合物 {Cp*M[N(i-Pr)C(Me)N(i- Pr)]}(2)(mu-eta(1):eta(1)-N(2)) (6, M = Mo) 和 (8, M = W)。Cp*Mo[N(i-Pr)C(NMe(2))N(i-Pr)]Cl(2) (4) 与 3 当量的 KC(8) 在 THF 中的化学还原同样产生抗磁性 {Cp* Mo[N(i-Pr)C(NMe(2))N(i-Pr)]}(2)(mu-eta(1):eta(1)-N(2)) (7)。7 和 8 的单晶 X 射线分析证实了双核端桥式 mu-eta(1):eta(1)-N(2) 配位模式和这些化合物的固态分子结构提供了

  DOI：

  10.1021/ja100469f

文献信息

• Metal-Mediated Production of Isocyanates, R₃ENCO from Dinitrogen, Carbon Dioxide, and R₃ECl
  作者：Andrew J. Keane、Wesley S. Farrell、Brendan L. Yonke、Peter Y. Zavalij、Lawrence R. Sita

  DOI：10.1002/anie.201502293

  日期：2015.8.24

  A highly efficient and versatile chemical cycle has been developed for the production of isocyanates through the molecular fixation of N2, CO2 and R3ECl (E=C, Si, and Ge). Key steps include a ‘one‐pot’ photolytic NN bond cleavage of a Group 6 dinuclear dinitrogen complex with in situ trapping by R3ECl to provide a metal terminal imido complex that can engage in simultaneous nitrene‐group transfer

  通过N 2，CO 2和R 3 ECl（E = C，Si和Ge）的分子固定，已开发出一种高效且通用的化学循环来生产异氰酸酯。关键步骤包括第6组双核二氮配合物的'一锅式'光解NN键裂解，并通过R 3 ECl原位捕获，以提供金属末端亚氨基配合物，该配合物可同时参与亚氮基转移和氧原子。转移生成中间金属末端羰基配合物，并释放出异氰酸酯产物。含氧配合物与额外当量的R 3 ECl反应生成二氯化金属，它是双核二氮原料的前体。
• Catalytic Degenerate and Nondegenerate Oxygen Atom Transfers Employing N2O and CO2 and a MII/MIV Cycle Mediated by Group 6 MIV Terminal Oxo Complexes
  作者：Brendan L. Yonke、Jonathan P. Reeds、Peter Y. Zavalij、Lawrence R. Sita

  DOI：10.1002/anie.201106074

  日期：2011.12.16

  Green oxidation: A new class of Group 6 metal complexes catalyzes the direct oxidation of isocyanides through nondegenerate oxygen atom transfer (OAT) utilizing N2O as a chemical oxidant. In addition they serve as photocatalysts for the reversible degenerate OAT between CO and CO2 (see scheme).

  绿色氧化：新型的第6组金属络合物利用N 2 O作为化学氧化剂，通过非简并的氧原子转移（OAT）催化异氰酸酯的直接氧化。此外，它们还用作CO和CO 2之间可逆的简并OAT的光催化剂（请参阅方案）。
• Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle
  作者：Jonathan P. Reeds、Brendan L. Yonke、Peter Y. Zavalij、Lawrence R. Sita

  DOI：10.1021/ja208669s

  日期：2011.11.23

  In the presence of CO, facile N-N bond cleavage of N(2)O occurs at the formal Mo(II) center within coordinatively unsaturated mononuclear species derived from Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](CO)(2) (Cp* = η(5)-C(5)Me(5)) (1) and Cp*Mo[N((i)Pr)C(Me)N((i)Pr)]}(2)(μ-η(1):η(1)-N(2)) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N((i)Pr)C(Me)N((i

  在 CO 存在下，N(2)O 的容易的 NN 键断裂发生在来自 Cp*Mo[N((i)Pr)C(Me)N((( i)Pr)](CO)(2) (Cp* = η(5)-C(5)Me(5)) (1) 和 Cp*Mo[N((i)Pr)C(Me)N ((i)Pr)]}(2)(μ-η(1):η(1)-N(2)) (9) 分别在光解和黑暗条件下产生亚硝酰基异氰酸酯复合物 Cp*Mo [N((i)Pr)C(Me)N((i)Pr)](κ-N-NO)(κ-N-NCO) (7)。N(2)O 的竞争性 NO 键断裂在相同条件下进行，得到 Mo(IV) 末端金属氧配合物 Cp*Mo[N((i)Pr)C(Me)N((i)Pr)]( O) (3)，它可以通过 CO 的氧原子转移氧化产生 CO(2) 来回收以产生更多的 7。
• Catalytic Production of Isocyanates via Orthogonal Atom and Group Transfers Employing a Shared Formal Group 6 M(II)/M(IV) Redox Cycle
  作者：Brendan L. Yonke、Jonathan P. Reeds、Philip P. Fontaine、Peter Y. Zavalij、Lawrence R. Sita

  DOI：10.1021/om500532s

  日期：2014.7.14

  Under an atmosphere of CO, the Mo(IV) imido complex Cp*Mo[N(Pr-i)C(Me)N(Pr-i)] (NSiMe3) (Cp* = eta(5)- C5Me5) (1) serves as a catalyst for production of an isocyanate via metal-mediated nitrene group transfer in benzene solution under mild conditions (55 degrees C, 10 psi) according to RN3 + CO -> N-2 + RNCO. Mechanistic and structural studies support a catalytic cycle for nitrene group transfer involving formal Mo(II) monocarbonyl and Mo(IV) (kappa(2)-C,N)-isocyanate intermediates. These results complement an earlier finding that catalytic production of isocyanates can alternatively proceed through oxygen-atom transfer and an isomeric Mo(IV) (kappa(2)-C,O)-isocyanate according to N2O + CNR -> N-2 + RNCO.