[Nb(η5-C5H4SiMe3)2(H)(cyclohexylisocyanido)] | 184172-12-1

• 英文名称: [Nb(η5-C5H4SiMe3)2(H)(cyclohexylisocyanido)]
• 英文别名: Nb(η(5)-C5H4SiMe3)2(H)(CN-cyclo-C6H11)；Nb(η(5)-C5H4SiMe3)2(H)(CNC6H11)；[Nb(η5-C5H4SiMe3)2(H)(CNCy)]
• CAS: 184172-12-1
• 化学式: C₂₃H₃₈NNbSi₂
• 分子量: 477.639
• InChiKey: RESHYGXSWIQARN-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-C5H4SiMe3)2(H)(cyclohexylisocyanido)] 、 三氟乙酸 以 氘代丙酮 为溶剂， 生成
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja9640354
• 作为产物：
  描述：

  异氰环已烷 、 Nb(η5-C5H4SiMe3)2H3 以 四氢呋喃 为溶剂， 以95%的产率得到[Nb(η5-C5H4SiMe3)2(H)(cyclohexylisocyanido)]
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/ja9640354

文献信息

• 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''=
• Synthesis, Characterization, and Reactivity of Isocyanidephosphidoniobocene Derivatives:  X-ray Diffraction Structures of New Isocyanideniobocene Complexes, [Nb(η⁵-C₅H₄SiMe₃)₂(CNR)(PMePh₂)]I, R = Xylyl, Cy
  作者：Antonio Antiñolo、David Evrard、Santiago García-Yuste、Antonio Otero、Juan C. Pérez-Flores、Rebeca Reguillo-Carmona、Ana M. Rodríguez、Elena Villaseñor

  DOI：10.1021/om060283p

  日期：2006.7.1

  atom directly bonded to the phosphorus. The cationic d2 species [Nb(η5-C5H4SiMe3)2(PRPh2)(L)]X [R = Me, X = I, L = CNBun (10), CNCy (11), and CNXylyl (12); R = CH2Ph, X = Br, CNBun (13), CNCy (14), and CNXylyl (15); R = CH2CH2Ph, X = Br, CNBun (16), CNCy (17), and CNXylyl (18)] were prepared by the reaction of alkyl halides RX (R = Me, X = I; CH2Ph, X = Br; CH2CH2Ph, X = Br) with 7, 8, or 9 by electrophilic

  氢化物niobocene络合物的反应[Nb的（η 5 -C 5 H ^ 4森达3）2 H（L）] [L = CNBu Ñ（1），CNCy（2），和CNXylyl（3）]与ClPPh 2得到阳离子niobocene配合物[Nb的（η 5 -C 5 H ^ 4森达3）2（PHPh 2）（L）]氯[L = CNBu ñ（4），CNCy（5），和CNXylyl（6）]。这些配合物用NaOH处理产生phosphidoniobocene衍生物[铌（η的一个新家族5 -C 5 H ^ 4森达3）2（PPH 2）（L）] [L = CNBu Ñ（7），CNCy（8），和CNXylyl（9）]通过消除与磷直接键合的氢原子。阳离子d 2种[Nb的（η 5 -C 5 H ^ 4森达3）2（PRPh 2）（L）] X [R = Me中，X = I，L = CNBu Ñ（10），CNCy（11）和CNXylyl（12）;
• 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
• Studies on the reactivity of Nb(η5-C5H4SiMe3)2(X)(L), X=H,Cl; L=CNXylyl, CNCy, CO and Nb(η5-C5H4SiMe3)2(H)3 complexes toward the Lewis acids B(C6F5)3 and BF3
  作者：Antonio Antiñolo、Fernando Carrillo-Hermosilla、Juan Fernández-Baeza、Santiago Garcı́a-Yuste、Antonio Otero、Javier Sánchez-Prada、Elena Villaseñor

  DOI：10.1016/s0022-328x(00)00107-8

  日期：2000.9

  The reaction of the electron-rich, coordinatively saturated, :niobocene-hydride or -halide complexes Nb(eta(5)-C5H4SiMe3)(2)(X)(L), X = H or Cl, L = 2,6-dimethylphenylisocyanide (CNXylyl), cyclohexylisocyanide (CNCy) and carbonyl (CO), with the strong Lewis acid (B(C6F5)(3)) gives the zwitterionic compounds [(eta(5)-C5H4SiMe3)(2)(CNXylyl)Nb(mu-X)(B(C6F5)(3)] (1), [(eta(5)-C5H4SiMe3)(2)(CNCy)Nb(mu-X)(B(C6F5)(3)] (2), [(eta(5)-C5H4SiMe3)(2)(CO)Nb(mu-X) (B(C6F5)(3))] (3), respectively, where the complexes possess a bridging hydride or halide group. Similarly, the starting niobocene-hydride species react with BF3 to afford the corresponding zwitterionic complexes containing a bridging hydride ligand, namely [eta(5)-C5H4SiMe3)(2)(CNXylyl)Nb(mu-H)(BF3)] (4), [(eta(5)-C5H4SiMe3)(2)(CNCy)Nb(mu-H)(BF3)] (5), [(eta(5)-C5H4SiMe3)(2)(CO)Nb(mu-H)(BF3)] (6). The reaction of the hydride containing compounds 1-3 with the appropriate ligand L (1:1 molar ratio for 1 and 2) in toluene at room temperature leads to the ionic compounds [(eta(5)-C5H4SiMe3)(2)Nb(CNXylyl)(2)][(HB(C6F5)(3))] (7), [(eta(5)-C5H4SiMe3)(2)Nb(CNCy)(2)][(HB(C6F5)(3))] (8), and [(eta(5)-C5H4SiMe3)(2)Nb(CO)(2)][(HB(C6F5)(3))] (9), which contain two coordinated L ligands and a noncoordinated [(HB(C6F5)(3))](-) counteranion. Analogous complexes were not observed in the same reaction for 4-6. Finally, the compound [Nb(eta(5)-C5H4SiMe3)(2)(H)(3)] reacts in acetone with (B(C6F5)(3)) in a clean reaction to give the ionic compound [(eta(5)-C5H4SiMe3)(2)Nb][((CH3)(2)CHO)B(C6F5)(3))] (10), which contains the isopropoxide berate ion [((CH3)(2)CHO)B(C6F5)(3))](-) as the counteranion. (C) 2000 Elsevier Science S.A. All rights reserved.