Nb(η5-(trimethylsilyl)cyclopentadienyl)2(H)(CN(2,6-(CH3)2C6H3)) | 184172-09-6

• 英文名称: Nb(η5-(trimethylsilyl)cyclopentadienyl)2(H)(CN(2,6-(CH3)2C6H3))
• 英文别名: Nb(η(5)-C5H4SiMe3)2(H)(CN(2,6-Me2C6H3))；Nb(η(5)-C5H4SiMe3)2(H)(CN-2,6-xylyl)；Nb(η(5)-C5H4SiMe3)2(H)(CNC6H3Me2)；(η5-C5H4SiMe3)2Nb(H)(CNC6H3-2,6-Me2)
• CAS: 184172-09-6
• 化学式: C₂₅H₃₆NNbSi₂
• 分子量: 499.645
• InChiKey: VWJXZHLHLJAUFR-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：

  Nb(η5-(trimethylsilyl)cyclopentadienyl)2(H)(CN(2,6-(CH3)2C6H3)) 、 2-巯基苯并噻唑 以 四氢呋喃 为溶剂， 以85%的产率得到(η5-C5H4SiMe3)2Nb(CNC6H3-2,6-Me2)(κ1-2-mercaptobenzothiazole(1-))
  参考文献：
  名称：

  Heterocycle-containing niobocene derivatives from hydride–niobocene complexes

  摘要：

  The reaction under thermal conditions Of [CP ' Nb-2(H)(3)] (1), Cp ' = eta(5)-C5H4SiMe3, with benzothiazole heterocycles, namely 2-aminobenzothiazole, bzta-NH2, 2-hydroxybenzothiazole, bzta-OH, 2-mercaptobenzothiazole, bzta-SH, benzoxazole, namely 2-mercaptobenzoxazole, bzoa-SH, and triazines, namely 1,3,5-triaminetriazine, 1,3,5-trihydroxytriazine, 1,3,5-trimercaptotriazine, (C3N3)-1,3, 5-(XH)(3), X = NH, O, S, yields a new family of niobocene complexes [CP ' Nb-2(kappa(2)-X,S-Xbzta)], X = NH (2), O (3), S (4), [CP ' Nb-2-( k(2)-S,N-Sbzoa)] (5) and [(CP ' Nb-2)(3)(kappa(2)-X,N-X3C3N3)], X = NH (6), X = O (7), X = S (8). In the same way, the thermal treatment of complex [CP ' Nb-2(H)(CNXylyl)] (9), Xylyl = C6H4-2,6-Me-2,, with bzta-SH, bzoa-SH and (C3H3)-1,3,5-(SH) affords the complexes [CP ' Nb-2(kappa(1)-S-Sbzta)(CNXylyl)] (10), [CP ' Nb-2(kappa(1)-S-Sbzoa)(CNXylyl)] (11) and [{CP ' Nb-2(CNXylyl)}(3)(kappa(1)-S-S3C3N3)] (12). The reaction of compound 10 with an excess of MeI in toluene at room temperature leads to the ionic compound [CP ' Nb-2(CNXylyl)(2)][I-3] (15), which contains two coordinated CNXylyl ligands and a non-coordinated I-3(-) counteranion. All complexes were characterized by spectroscopic methods and the molecular structure of [CP ' Nb-2(CNXylyl)(2)][I-3] (15) and [CP ' Nb-2(H)(P(OMe)(3))] (.) (bzta)'-NH2 (14), an adduct of the heterocycle with the hydride-niobocene, have been determined by X-ray molecular studies. (c) 2007 Elsevier B.V.. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.03.038
• 作为产物：
  描述：

  Nb(η(5)-C5H4SiMe3)2(H)2(SiPh3) 、 2,6-二甲基苯基异腈 以 甲苯 为溶剂， 生成 Nb(η5-(trimethylsilyl)cyclopentadienyl)2(H)(CN(2,6-(CH3)2C6H3))
  参考文献：
  名称：

  第一铌茂金属锗配合物的合成，表征以及三苯基甲硅烷基，三苯基锗基和三苯基锡烷基铌茂世衍生物的反应性。d的透视分子结构0的Nb（η 5 -C 5 H ^ 4森达3）2（H）2（弗3）（E =锗，锡）

  摘要：

  铌的热处理（η 5 -C 5 H ^ 4森达3）2（H）3（1）与适当的有机锗氢化物（HGeR 3）和HSnPh 3给出了相应的niobocene甲锗烷基铝氢化物的Nb（η 5 -C 5 H ^ 4 SiMe 3）2（H）2（GeR 3），GeR 3 GePh 3（2），GePh 2 H（3），GeEt 3（4），Ge（C 6ħ 13）3（5），葛我难道3（我AM = CH 2 CH 2 CH（CH 3）2）（6），锗（C 6 H ^ 13）2 Cl（上7），葛我难道2 Cl（上8），锗（C 6 H ^ 13）2 H（9），葛我上午2 H（10），和Nb（η 5 -C 5 H ^ 4SiMe 3）2（H）2（SnPh 3）（11）的产率很高。光谱数据表明其中两个可能的结构异构体中仅一个存在，其中胚芽基或苯乙烯基在对称结构的赤道平面内。所述系列的Nb（η反应性研究5 -C 5 H ^ 4森达3）2（H）2（ER

  DOI：

  10.1021/om971001b

文献信息

• New reactivity of . Synthesis, electrosynthesis and reactivity of new carboxylato niobocene complexes
  作者：Antonio Antiñolo、Santiago García-Yuste、Isabel López-Solera、Antonio Otero、Juan Carlos Pérez-Flores、Isabel del Hierro、Laurent Salvi、Hélène Cattey、Yves Mugnier

  DOI：10.1016/j.jorganchem.2005.04.003

  日期：2005.7

  complexes, mononuclear Cp2′Nb(κ2-O,O′OOC(C6H5))(3), binuclear [(Cp2′Nb)2(1,4-(κ2-O,O′OOC)2(C6H4))](4)and[(Cp2′Nb)2(1,3-(κ2-O,O′OOC)2(C6H4))](5) and trinuclear [(Cp2′Nb)3(1,3,5-(κ2-O,O′OOC)3(C6H3))](6), have been prepared by the reaction of Cp2′NbH3(1) and the corresponding carboxylic acid, namely (C6H5)COOH, (1,4-COOH)2(C6H4), (1,3-COOH)2(C6H4) and (1,3,5-COOH)3(C6H3). Complexes 3, 4, 5 and 6 have been prepared

  一个新的含铌二齿羧基羧基的铌茂金属配合物新家族，单核Cp2'Nb（κ2-O，O'OOC（C6H5））（3），双核[（Cp2'Nb）2（1,4-（κ2-O， O'OOC）2（C6H4））]（4）和[（Cp2'Nb）2（1,3-（κ2-O，O'OOC）2（ ））]（5）和三核[[Cp2' Nb）3（1,3,5-（κ2-O，O'OOC）3（C6H3））]（6）是通过Cp2'NbH3（1）与相应的羧酸（即（ C 6 H 5）COOH，（1,4-COOH）2（C 6 H 4），（1,3-COOH）2（C 6 H 4）和（1,3,5-COOH）3（C 6 H 3）。配合物3，4，图5和图6已经通过另一种方法制备，该方法包括在相应的羧酸的适当摩尔比存在下，对Cp2'NbCl2（2）进行双电子还原。此外，复合物的反应3，4和6与2,6-ME 2 ç 6 ħ 3在摩尔比1 NC（xylylNC）：1，
• Studies on the Insertion Reactions of Activated Alkynes into Nb−H Bonds in Hydride−Niobocene Complexes. X-ray Crystal Structures of Nb(η⁵-C₅H₄SiMe₃)₂(H)[η²-RO₂C(H)C(H)CO₂R] (R = Me or ^<i>t</i>Bu)
  作者：Antonio Antiñolo、Fernando Carrillo-Hermosilla、Mariano Fajardo、Santiago García-Yuste、Maurizio Lanfranchi、Antonio Otero、Maria Angela Pellinghelli、Sanjiv Prashar、Elena Villaseñor

  DOI：10.1021/om9605241

  日期：1996.12.24

  MeO2CC⋮CH to give the hydride olefin derivatives, Nb(η5-C5H4SiMe3)2(H)[η2-RO2C(H)C(H)CO2R‘], R = R‘ = Me 13; R = R‘ = tBu 14; and Nb(η5-C5H4SiMe3)2(H)[η2-MeO2C(H)CH2] 15, probably as the result of a stereospecific trans-insertion. The different complexes have been characterized by spectroscopic methods. In addition, the structure of 13 and 14 were determined by single crystal X-ray diffraction.

  氢化物胩络合物，铌（η 5 -C 5 H ^ 4森达3）2（H）（CNR），R =二甲苯基= 2,6-二甲基苯基; Cy（环己基）; t Bu; 以及氢化羰基络合物的Nb（η 5 -C 5 H ^ 4森达3）2（H）（CO）与几个活化的炔烃，得到反应的相应的烯基胩络合物的Nb（η 5 -C 5 H ^ 4森达3）2（CNR）（C（R'）CH（R''）），R =二甲苯基，R'= R''= CO 2 Me 1; R =二甲苯基，R'= R''= CO 2 t Bu 2；R ＝二甲苯基，R′＝ CO 2 Me，R″ ＝ H 3；R ＝ H 2。R =二甲苯基，R'= CO 2 Me，R''= Me 4；R = Cy，R'= R''= CO 2 Me 5；R = Cy，R'= R''= CO 2 t Bu 6；R = Cy，R'= CO 2 Me，R''= Me 7；R = t Bu，R'= R''=
• Structure and Dynamics of [Nb(η⁵-C₅H₄SiMe₃)₂(η²-H₂BR₂)] (R₂ = O₂C₆H₄, C₈H₁₄, H₂) Complexes. A Combined Experimental and Theoretical Study
  作者：Antonio Antiñolo、Fernando Carrillo-Hermosilla、Juan Fernández-Baeza、Santiago García-Yuste、Antonio Otero、Ana María Rodríguez、Javier Sánchez-Prada、Elena Villaseñor、Ricard Gelabert、Miquel Moreno、José M. Lluch、Agustí Lledós

  DOI：10.1021/om000221d

  日期：2000.9.1

  niobocene complexes [Nb(η5-C5H4SiMe3)2(η2-H2BR2)] (R2 = O2C6H4 (1), C8H14 (2), H2 (3)). The reaction with H2BO2C6H4 or H2BC8H14 proceeds at mild temperature, and the BH3·THF adduct reacts even at low temperature. Complexes 2 and 3 show dynamic behavior in solution. Spectroscopic and theoretical studies were carried out in order to clarify these dynamic processes. In addition, X-ray diffraction studies of

  从niobocene三氢化CP的反应二氢消除“ 2 NBH 3（CP” =η 5 -C 5 H ^ 4森达3）及相应的硼烷提供了一种合成途径到新的含硼酸盐niobocene配合物[Nb的（η 5 - ç 5 ħ 4森达3）2（η 2 -H 2 BR 2）]（R 2 = O 2 C ^ 6 ħ 4（1），C 8 H ^ 14（2），H2（3））。与H 2 BO 2 C 6 H 4或H 2 BC 8 H 14的反应在温和的温度下进行，并且即使在低温下，BH 3 ·THF加合物也会反应。配合物2和3显示了溶液中的动态行为。为了阐明这些动态过程，进行了光谱和理论研究。另外，进行了2次的X射线衍射研究，其结果与理论数据相关。最后，CP”的反应2的Nb（H）（L）（L = CO，CN（2,6-ME 2 Ç 6H 3），t BuOOCH CHCOO t Bu）与BH 3 ·THF生成配合物3，同时消除了合适的辅助配体L。
• Insertion reactions of heterocumulenes into the niobium-hydride bond of isocyanide and carbonyl niobocene complexes
  作者：Antonio Antiñolo、Fernando Carrillo-Hermosilla、Santiago Garcia-Yuste、Manuel Freitas、Antonio Otero、Sanjiv Prashar、Elena Villaseñor、Mariano Fajardo

  DOI：10.1016/s0020-1693(96)05587-9

  日期：1997.6

  The reaction of the hydride niobocene complexes, Nb(η5-C5H4SiMe3)2(H)(CNR) (R=2,6-dimethylphenyl (Xyiyl) orcyclohexyl (Cy)) and Nb(η5-C5H4SiMe3)2(H)(CO) with the heterocumulenes PhN=C=X (X=0 or S) affords the new formamido and thioformamido complexes Nb((η5-C5H4SiMe3)2)2(CNR)(η1-XC(H)NPh) (R=Xylyl, X=0 (1); R=Xylyl, X=S (2); R=Cy, X =O (3); R-Cy, X=S (4)) and Nb((η5-C5H4SiMe3)2) 2(CO) (η1-XC(H) NPh)

  氢化物niobocene复合物的反应，铌（η 5 -C 5 H ^ 4森达3）2（H）（CNR）（R = 2,6-二甲基苯基（Xyiyl）orcyclohexyl（CY））和Nb（η 5 -C 5 ħ 4森达3）2（H ^）（CO）与heterocumulenes PHN = C = X（X = O或S），得到新的和甲酰络合物thioformamido的Nb（（η 5 -C 5 H ^ 4森达3）2）2（CNR）（η 1-XC（H）NPh）（R =二甲苯基，X = 0（1）; R =二甲苯基，X = S（2）; R = Cy，X = O（3）; R-Cy，X = S（4 ））和Nb（（η 5 -C 5 H ^ 4森达3）2）2（CO）（η1-XC（H）NPH）（X = 0（5）; X = S（6））。使用HCF3COO这些衍生物的质子化产生了trifluoroacetato络合物的Nb（（η
• Synthesis and Spectroscopic Properties of Dihydrogen Isocyanide Niobocene [Nb(η⁵-C₅H₄SiMe₃)₂(η²-H₂)(CNR)]⁺ Complexes. Experimental and Theoretical Study of the Blocked Rotation of a Coordinated Dihydrogen
  作者：Antonio Antiñolo、Fernando Carrillo-Hermosilla、Mariano Fajardo、Santiago Garcia-Yuste、Antonio Otero、Santiago Camanyes、Feliu Maseras、Miquel Moreno、Agustí Lledós、José M. Lluch

  DOI：10.1021/ja9640354

  日期：1997.7.1

  Synthesis of stable hydride isocyanide derivatives Nb(eta(5)-C5H4SiMe3)(2)(H)(CNR) has been achieved through the formation of coordinatively unsaturated 16-electron species Nb(eta(5)-C5H4SiMe3)(2)H by thermolytic loss of H-2 followed by the coordination of an isocyanide ligand. Low-temperature protonation with a slight excess of CF3COOH leads to the eta(2)-dihydrogen complexes [Nb(eta(5)-C5H4SiMe3)(2)(eta(2)-H-2)(CNR)](+). NMR spectra of these H-H complexes and their monodeuterated H-D isotopomers present a single high-field resonance at room temperature. By lowering the temperature to 178 K, decoalescence of the signal was observed for the H-D complexes but not for the H-H ones. By combining DFT electronic structure calculations with a monodimensional rotational tunneling model, it has been shown that the absence of decoalescence of the H-H signal is due to the existence of a very large exchange coupling. Conversely, for the H-D isotopomer, the difference in zero point energy corresponding to two nonequivalent (H-D and D-H) positions leads to a slight asymmetry which dramatically reduces the exchange coupling, allowing decoalescence to be observed. Therefore, the H-D classical rotation and the quantum exchange processes will not be practically observed for this complex, whereas only the classical process for the H-H species is quenched out on the NMR time scale.