isocyanocyclohexane;tribromoniobium | 245411-07-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: isocyanocyclohexane;tribromoniobium
• CAS: 245411-07-8
• 化学式: C₂₈H₄₄Br₃N₄Nb
• 分子量: 769.303
• InChiKey: BHGZGUMPLBZYKX-UHFFFAOYSA-K

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

• 作为产物：
  描述：

  异氰环已烷 、 NEt4{Nb(CO)6} 、 溴 以 四氢呋喃 为溶剂， 以82%的产率得到isocyanocyclohexane;tribromoniobium
  参考文献：
  名称：

  Isocyanide–Group 5 complexes and metal-centred C–C coupling

  摘要：

  The Nb-I complexes [XNb(CO)(2)(CNR)(4)] (X = I, Br; R = tBu, cHex, 2,6-Me2C6H3) (4) have been identified as intermediates in the system [Nb(CO)(6)](-)/CNR/X-2, which generates the Nb-III complexes [I2Nb(CNR)(6)]I (1) and [X3Nb(CNR)(3)] (2) or, on addition of tolane, [I2Nb(CNtBu)(3)tolane]I (3). In the presence of small amounts of water, the aminoalkyne-Nb-III complexes [X2Nb(CNR)(4)RHNC=CNHR]X (R = tBu; X = I: 5a, X = Br: 5b) are formed. The complex 4a (X = I, R = tBu) converts to 5a in the presence of water, suggesting successive protonation and intramolecular reductive isocyanide coupling mediated by the Nb-I centre. The V-I complexes [XV(CO)(2)(CNR)(2)dppe] (X = I, R = tBu, cHex; X = Br, R = tBu) (6) and the V-III complex [I2V(CNtBu)(6)]I (7) have been obtained from the system [V(CO)(6)](-)/CNR/X-2 in dry THF, while the coupling product [I2V(CNtBu)(4)tBuHNC=CNHtBu]I (8) is recovered as water is added. In contrast to the Nb system, V-II complexes of composition [I2V(CNR)(4)] (9) and [I2V(CNtBu)(2)(PR3)(2)] (10) can also be synthesised. The complex 10b (PR3 = PPhMe2) has also been prepared from cis-[V(CO)(4)(PPhMe2)(2)](-) (11). The system [Ta(CO)(6)](-)/CNtBu/I-2 yielded the complexes [ITa(CO)(3)(CNtBu)(3)] (13a), [ITa(CO)(3)(CNtBu)dppe] (13b) and [I2Ta(CNtBu)(6)]I (14). The chloro-isocyanide complexes [Cl2V(CCPh)(CNtBu)(2)] (12) and [Cl2Ta(CNcHex)(4)] (15) have been generated from the metal chlorides as starting products. [INb(CO)(2)(CNtBu)(4)]. 2toluene (4a.2toluene), trans-[I2V{CN(2,6-Me2C6H3}(4)] (9a) and cis-[Et4N][V(CO)(4)(PPhMe2)(2)] ([Et4N]-11) have been characterised by single-crystal X-ray diffraction. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00240-5