Nb(hydride)(η2-(t-Bu)CHN(3,5-C6H3Me2))(N[CH2(t-Bu)](3,5-C6H3Me2))2 | 521085-27-8

• 英文名称: Nb(hydride)(η2-(t-Bu)CHN(3,5-C6H3Me2))(N[CH2(t-Bu)](3,5-C6H3Me2))2
• 英文别名: NbH(η2-N(3,5-dimethylphenyl)CHtBu)(N(3,5-dimethylphenyl)CH2tBu)2；[Nb(H)(η2-(CH3)3CCHN(3,5-Me2C6H3))(N(neopentyl)(3,5-Me2C6H3))2]；Nb(H)(η2-t-Bu(H)C=N-3,5-Me2C6H3)(N[neopentyl]-3,5-Me2C6H3)2；HNb(η2-tBuHC=N(3,5-C6H3Me2))(N(CH2tBu)(3,5-C6H3Me2))2；Nb(H)(t-Bu(H)C=N-3,5-Me2C6H3)(N[neopentyl]-3,5-Me2C6H3)2
• CAS: 521085-27-8
• 化学式: C₃₉H₆₀N₃Nb
• 分子量: 663.832
• InChiKey: FWDBRHWRKHJXIU-RTELBWHMSA-N

计算性质

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

• 作为反应物：
  描述：

  Nb(hydride)(η2-(t-Bu)CHN(3,5-C6H3Me2))(N[CH2(t-Bu)](3,5-C6H3Me2))2 以 氘代苯 为溶剂， 生成 [Nb(neopentylimido)(3,5-Me2C6H3)(N(neopentyl)(3,5-Me2C6H3))2]
  参考文献：
  名称：

  The Niobaziridine−Hydride Functional Group:  Synthesis and Divergent Reactivity

  摘要：

  A multistep synthetic strategy enables the isolation of the niobaziridine-hydride complex Nb(H)(eta2-tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-C6H3Me2), which functions as a reactive synthon for its tautomer, the three-coordinate, trisamide species Nb(N[Np]Ar)3 (2). Treatment of 1 with various small molecules has demonstrated its capacity to effect two-electron reduction chemistry. Most noteworthy is the reaction between 1 and elemental phosphorus (P4), providing in high yield the bridging diphosphide complex (mu2:eta2,eta2-P2)[Nb(N[Np]Ar)3]2. However, unsaturated organic functionality including nitriles and aldehydes can insert into the Nb-H bond of 1, leaving the niobaziridine ring intact, thus demonstrating that dual pathways of reactivity are available to the niobaziridine-hydride functional group.

  DOI：

  10.1021/ja028446y
• 作为产物：
  描述：

  [NbI2(N(neopentyl)(3,5-Me2C6H3))3] 在 Mg(THF)4(anthracene) 作用下， 以 四氢呋喃 为溶剂， 以45%的产率得到Nb(hydride)(η2-(t-Bu)CHN(3,5-C6H3Me2))(N[CH2(t-Bu)](3,5-C6H3Me2))2
  参考文献：
  名称：

  The Niobaziridine−Hydride Functional Group:  Synthesis and Divergent Reactivity

  摘要：

  A multistep synthetic strategy enables the isolation of the niobaziridine-hydride complex Nb(H)(eta2-tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-C6H3Me2), which functions as a reactive synthon for its tautomer, the three-coordinate, trisamide species Nb(N[Np]Ar)3 (2). Treatment of 1 with various small molecules has demonstrated its capacity to effect two-electron reduction chemistry. Most noteworthy is the reaction between 1 and elemental phosphorus (P4), providing in high yield the bridging diphosphide complex (mu2:eta2,eta2-P2)[Nb(N[Np]Ar)3]2. However, unsaturated organic functionality including nitriles and aldehydes can insert into the Nb-H bond of 1, leaving the niobaziridine ring intact, thus demonstrating that dual pathways of reactivity are available to the niobaziridine-hydride functional group.

  DOI：

  10.1021/ja028446y

文献信息

• Properties and Reactivity Patterns of AsP₃: An Experimental and Computational Study of Group 15 Elemental Molecules
  作者：Brandi M. Cossairt、Christopher C. Cummins

  DOI：10.1021/ja906294m

  日期：2009.10.28

  and structural characterization of AsP(3)(P(N((i)Pr)(2))N(SiMe(3))(2))(2), 2, and activations of AsP(3) by reactive early transition-metal fragments including Nb(H)(eta(2)-(t)Bu(H)C horizontal lineNAr)(N[CH(2)(t)Bu]Ar)(2) and Mo(N[(t)Bu]Ar)(3) (Ar = 3,5-Me(2)C(6)H(3)). In the presence of reducing equivalents, AsP(3) was found to allow access to [Na][E(3)Nb(ODipp)(3)] (Dipp = 2,6-diisopropylphenyl) complexes

  对可分离、耐热性强的 AsP(3) 分子的轻松合成访问允许对其物理性质和反应化学与各种过渡金属和有机碎片进行彻底研究。AsP(3) 与 P(4) 相比的电子特性由 DFT 和分子中的原子 (AIM) 方法揭示，并就观察到的电化学配置文件和两个分子的磷 NMR 特性进行了讨论。核独立化学位移的调查显示 AsP(3) 保留球形芳香。描述了 AsP(3) 和 P(4) 的热力学特性。本研究中探索的反应类型包括 AsP(3) 四面体对其元素的热分解、[(AsP(3))FeCp*(dppe)][BPh(4)] (dppe = 1、2-双（二苯基膦）乙烷），1，选择性单 As-P 键裂解反应，包括 AsP(3)(P(N((i)Pr)(2))N(SiMe(3) 的合成和结构表征))(2))(2), 2 和 AsP(3) 的活化，包括 Nb(H)(eta(2)-(t)Bu(H)C 水平线 NAr)(N [CH(2)(t)Bu]Ar)(2)
• Phosphaalkynes from Acid Chlorides via P for O(Cl) Metathesis:  A Recyclable Niobium Phosphide (P^3-) Reagent that Effects C−P Triple-Bond Formation
  作者：Joshua S. Figueroa、Christopher C. Cummins

  DOI：10.1021/ja0461522

  日期：2004.11.1

  recovered after vacuum transfer and can be treated with 1.0 equiv of triflic anhydride (Tf2O, Tf = O2SCF3) to afford the bistriflate complex, Nb(OTf)2(N[Np]Ar)3 (7), in high yield. Complex 7 provides direct access to 1 upon reduction with magnesium anthracene, thus completing a cycle of element activation, small-molecule generation via metathetical P-atom transfer, and deoxygenative recycling of the final

  本文报道了一种新的复分解 P 用于 O(Cl) 交换，由阴离子磷化铌配合物介导，该配合物在温和条件下由酰氯 (RC(O)Cl) 提供磷炔 (RCP)。niobaziridine 氢化物复合物 Nb(H)(tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = 新戊基，Ar = 3,5-Me2C6H3)，先前已显示与元素反应磷 (P4)，提供 mu-二磷化物复合物，(mu2:eta2,eta2-P2)[Nb(N[Np]Ar)3]2, (2)，随后可以通过钠汞合金将其还原为阴离子，末端磷化物络合物，[Na][PNb(N[Np]Ar)3] (3)。现在表明，用新戊酰 (t-BuC(O)Cl) 或 1-金刚酰 (1-AdC(O)Cl) 氯化物处理 3 可提供热不稳定的铌酸，(t-BuC(O)P)Nb (N[Np]Ar)3 (4-t-Bu) 和 (1-AdC(O)P)Nb(N[Np]Ar)3
• Triple-Bond Reactivity of an AsP Complex Intermediate: Synthesis Stemming from Molecular Arsenic, As₄
  作者：Heather A. Spinney、Nicholas A. Piro、Christopher C. Cummins

  DOI：10.1021/ja906550h

  日期：2009.11.11

  a terminal arsenide anion complex of niobium. Functionalization of the latter provides the new AsPNMes* ligand, which when complexed with tungsten pentacarbonyl elicits extrusion of the (AsP)W(CO)(5) molecule as a reactive intermediate. Trapping reactions of the latter with organic dienes are found to furnish double Diels-Alder adducts in which the AsP unit is embedded in a polycyclic organic framework

  虽然 P(4) 是磷的稳定分子形式，但最近的一项研究说明了在温和条件下有机介质中反应生成 P(2) 的可能性。较重的第 15 族元素砷可以作为 As(4) 分子存在，但 As(4) 不能作为纯物质储存，因为它既对光敏感，又在热时恢复为稳定的金属灰色形式。在本文中，我们报告了 As(4) 活化，产生了 mu-As(2) 铌复合物，进而作为铌的终端砷化物阴离子复合物的前体。后者的功能化提供了新的 AsPNMes* 配体，当与五羰基钨复合时，会引起 (AsP)W(CO)(5) 分子作为反应中间体的挤出。发现后者与有机二烯的捕集反应提供双 Diels-Alder 加合物，其中 AsP 单元嵌入多环有机骨架中。(AsP)W(CO)(5) 在与 Mo(N[(i)Pr]Ar)(3) 相同的中性末端磷化物复合物 P 存在下的热生成导致环-AsP(2) 复合物 (OC )(5)W(cyclo-AsP(2))
• Carbon Dioxide Reduction by Terminal Tantalum Hydrides: Formation and Isolation of Bridging Methylene Diolate Complexes
  作者：Matthew A. Rankin、Christopher C. Cummins

  DOI：10.1021/ja104761n

  日期：2010.7.28

  and 2 are presented. Exposure of 1 to ca. 1 atm of CO(2) results in the production of methylene diolate complex (Ar[(t)BuCH(2)]N)(2)(eta(2)-(t)Bu(H)CNAr)Ta}(2)(mu-OCH(2)O) as a mixture of rac and meso diastereomers (3r,m). Similar reactivity for the Nb congener of 1 is reported herein. Further-more, methylene diolate complex (Ar[(t)BuCH(2)]N)(2)(kappa(2)-CH(2)C(Me)(2)CH(2)NAr)Ta}(2)(mu-OCH(2)O) (4)

  报道了钽氮杂-氢化物配合物 (Ar[(t)BuCH(2)]N)(2)(eta(2)-(t)Bu(H)CNAr)TaH (1) 的制备 (Ar = 3,5 -Me(2)C(6)H(3))。虽然在 -35 摄氏度的固态下可稳定数月，但在溶液中，该复合物会部分转化为异构氢化物 (Ar[(t)BuCH(2)]N)(2)(kappa(2)-CH(2) C(Me)(2)CH(2)NAr)TaH (2)。尽管 1 和 2 在苯溶液中处于平衡状态，但通过使用冷正戊烷进行选择性沉淀，可以将配合物 2 与 1 完全分离；介绍了 1 和 2 的固态结构。暴露于约 1。1 atm 的 CO(2) 导致生成亚甲基二醇络合物 (Ar[(t)BuCH(2)]N)(2)(eta(2)-(t)Bu(H)CNAr)Ta}( 2)(mu-OCH(2)O) 作为外消旋和内消旋非对映异构体 (3r,m) 的混合物。本文报道了 1
• Niobaziridine Hydrides
  作者：Joshua S. Figueroa、Nicholas A. Piro、Daniel J. Mindiola、Michael G. Fickes、Christopher C. Cummins

  DOI：10.1021/om100522p

  日期：2010.11.8

  Presented herein are synthetic, structural, and reactivity studies delineating the characteristics of the niobaziridine hydride functional group as it pertains to the stabilization of trisanilide niobium complexes of the type Nb(N[R]Ar)3 (1R, Ar = 3,5-Me2C6H3). Utilization of the N-isopropyl anilide ligand, N[i-Pr]Ar, results in the niobaziridine hydride dimer [Nb(H)(η2-Me2C═NAr)(N[i-Pr]Ar)2]2 ([2i-Pr-H]2)

  本文介绍了合成的，结构的和反应性的研究，它们描述了氢化尼巴齐啶氢化物官能团的特征，因为它与稳定Nb（N [R] Ar）3型三苯胺化物铌配合物有关（1 R，Ar = 3,5 -Me 2 C 6 H 3）。所述的利用Ñ -异丙基N-酰苯胺配体，N [我-Pr]的Ar，导致niobaziridine氢化物二聚物[铌（H）（η 2 -Me 2 C═NAr）（N [我-Pr] AR）2 ] 2（[ 2 i -Pr -H] 2）。二聚体[ 2我-Pr -H] 2是在室温下并分解经由热不稳定邻-metalation和我-Pr自由基喷射到含有铌的Nb键的种类。配位体变体N [Np个的Ar（NP =新戊基）提供了室温下为稳定的氢化物niobaziridine单体的Nb（H）（η 2 -吨-Bu（H）C═NAr）（N [Np个的Ar） 2（ 2 Np -H）。2 Np -H在高温（75°C）下的热分解提供了新