tridecahydro-7-t-butylammonio-7-carba-nido-undecaborate | 174872-06-1

• 英文名称: tridecahydro-7-t-butylammonio-7-carba-nido-undecaborate
• 英文别名: nido-7-NH2Bu(t)-7-CB10H12；7-NH2C(CH3)3-nido-7-CB10H12；7-NH2t-Bu-nido-7-CB10H12；7-NH2tBu-nido-7-CB10H12；nido-(t)BuH2N-7-CB10H12
• CAS: 174872-06-1
• 化学式: C₅H₂₃B₁₀N
• 分子量: 205.354
• InChiKey: UKLIESVROXMLIW-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：

  Wilkinson's catalyst 、 tridecahydro-7-t-butylammonio-7-carba-nido-undecaborate 以 甲苯 为溶剂， 以62%的产率得到[RhCl(PPh3)(η(5)-7-NH2Bu(t)-7-CB10H10)]
  参考文献：
  名称：

  Synthesis of Monocarbollide Complexes of Rhodium

  摘要：

  The compounds [RhX(PPh(3))(3)] react with nido-7-NH(2)Bu(t)-7-CB10H12 in toluene to give the 16-electron complexes [RhX(PPh(3))(eta(5)-7-NH(2)Bu(t)-7-CB10H10)] (1a, X = Br; 1b, X = Cl). The structure of the zwitterionic molecule 1a was determined by X-ray crystallography. Crystals are monoclinic, space group P2(1)/c, with a 12.937(3) Angstrom, b = 18.101(4) Angstrom, c = 14.695(4) Angstrom, beta = 104.21(2)degrees, and Z = 4. The metal atom is coordinated on one side by Br and PPh(3) groups and on the other in the pentahapto manner by the open CBBBB face of the cage system. Reactions of the complexes with several donor molecules have been investigated. With CNBu(t), by changing the stoichiometry or work-up procedures either the 18-electron complexes [RhX(CNBu(t))(PPh(3))(eta(5)-7-NH(2)Bu(t)-7-CB10H10)] (2a, X = Br; 2b, X = Cl) or [Rh(CNBu(t))(2)(PPh(3))(eta(5)-7-NHBu(t)-7-CB10H10)] (3) are obtained, or the 16-electron complex [Rh(CNBu(t))(PPh(3))(eta(5)-7-NHBu(t)-7-CB10H10)] (4) is formed. Formation of 3 and 4, in which the rhodium atoms are ligated by a nido-7-NHBu(t)-7-CB10H10 cage, formally a 3 pi-electron donor, is unusual and results from loss of HX from the precursors 1. To establish firmly the nature of these species, their molecular structures were determined by X-ray crystallography. Crystals of 3 are monoclinic, space group P2(1)/c, with a 10.533(2) Angstrom, b = 19.110(4) Angstrom, c = 19.707(4) Angstrom, beta = 105.413(9)degrees, and Z = 4, while those of 4 are triclinic, space group , with a = 9.840(3) Angstrom, b = 10.809(3) , c = 17.287(3) Angstrom, alpha = 88.49(2)degrees, beta = 84.57(2)degrees, gamma = 69.809(14)degrees, and Z = 2. The two molecular structures are very similar: the rhodium atom is attached on one side via an eta(5)-bonding mode to the open face of the 7-NHBu(t)-7-CB10H10 cage and on the other by the PPh(3) ligand and one or two CNBu(t) molecules, respectively. The reactions between the compounds 1 and PEt(3), PMe(3), NC(5)H(4)Me-4, and tetrahydrofuran (thf) give the complexes [RhBr(PEt(3))(eta(5)-7-NH(2)Bu(t)-7-CB10H10)] (5), [RhCl(PMe(3))(2)(eta(5)-7-NH(2)Bu(t)-7-CB10H10)] (6), and [RhBr(L)(eta(5)-7-NH(2)Bu(t)-7-CB10H10)] (7a, L = NC(5)H(4)Me-4; 7b, L = thf), respectively. Prolonged refluxing of mixtures of [CoCl(PPh(3))(3)] and nido-7-NH(2)Bu(t)-7-CB10H12 in toluene gives the arene(carborane)-cobalt complex [Co(eta(6)-C(6)H(5)Me)(eta(5)-7-NHBUt-7-CB10H10)] (8), the structure of which was determined by X-ray diffraction. Crystals are monoclinic, space group P2(1)/c, with a = 16.332(5) Angstrom, b = 10.397(2) A, 22.186(6) Angstrom, beta = 102.94(2)degrees, and Z = 8. NMR data for the new compounds are reported and discussed in relation to their structures.

  DOI：

  10.1021/ic951550e
• 作为产物：
  描述：

  decaborane 、 异氰酸叔丁酯 以 苯 为溶剂， 以90%的产率得到tridecahydro-7-t-butylammonio-7-carba-nido-undecaborate
  参考文献：
  名称：

  Deprotonation of the carbaborane nido-7-NH2But-7-CB10 H12: crystal structures of nido-7-NH2But-7-CB10 H12 and [NEt3(CH2Ph)][ nido-7-NHBut-7-CB10H12 ]

  摘要：

  通过 X 射线衍射测定了 nido-7-NH 2 Bu t -7-CB 10 H 12 1 的晶体结构。该化合物结晶于正交空间群 Pbca [a = 10.507(5)，b = 13.805(6)，c = 18.093(9)埃]。通过傅里叶差分图确定了两个内-B-H-B 和两个 NH 2 氢原子的位置，并对其进行了细化，从而确定了该化合物的二十面体结构。11 B-{ 1 H}- 11 B-{ 1 H} 相关核磁共振光谱也为结构的确定提供了支持。1 的分子轨道计算和前沿密度分析表明，去质子化最初应发生在外侧氮原子上。 用 1 个等量的 LiBu n 处理 1，然后加入 [NEt 3 (CH 2 Ph)]Cl，得到 [NEt 3 (CH 2 Ph)][nido-7-NHBu t -7-CB 10 H 12 ] 2 作为唯一的产物，并生长出单晶体进行 X 射线衍射研究。该盐在单斜空间群 P2 1 /n [a = 10.651(2)，b = 11.652(2)，c = 20.926(3)埃，β = 101.77(2)°]中结晶。1 H、13 C-{ 1 H} 和 11 B-{ 1 H} 的核磁共振谱。还记录了 1 和 2 的核磁共振光谱。

  DOI：

  10.1039/a607212g

文献信息

• A convenient cyanide-free “one-pot” synthesis of nido-Me3N-7-CB10H12 and nido-7-CB10H13−
  作者：Andrei S. Batsanov、Mark A. Fox、Andrés E. Goeta、Judith A. K. Howard、Andrew K. Hughes、John M. Malget

  DOI：10.1039/b200930g

  日期：——

  Reaction of nido-tBuH2N-7-CB10H12 with Na2CO3 and (MeO)2SO2 in THF results in mono-methylation to give nido-tBuMeHN-7-CB10H12, whilst prolonged reaction at elevated temperatures results in a quantitative yield of the tri-methyl derivative nido-Me3N-7-CB10H12, as a result of metathesis of the tert-butyl group. The 11B NMR spectrum of nido-tBuMeHN-7-CB10H12 is explored as a function of pH, demonstrating exchange with nido-tBuMeN-7-CB10H12−. Reaction of B10H14 with CyNC gives nido-CyH2N-7-CB10H12, which is methylated by Na2CO3 and (MeO)2SO2 in THF to give nido-CyMe2N-7-CB10H12. Deprotonation of nido-Me3N-7-CB10H12 and nido-CyMe2N-7-CB10H12 yields Na[nido-Me3N-7-CB10H11] and Na[nido-CyMe2N-7-CB10H11] respectively. Both trialkyl(amino)carboranes can be converted to Na[nido-CB10H13], itself a precursor to the poorly coordinating anion closo-CB11H12−. The molecular structures of nido-tBuMeHN-7-CB10H12 and nido-CyMe2N-7-CB10H12, determined by single crystal X-ray diffraction, are reported.

  nido-tBuH2N-7-CB10H12与Na2CO3和(MeO)2SO2在THF中的反应导致单甲基化，生成nido-tBuMeHN-7-CB10H12，而在高温下长时间反应则导致三甲基衍生物nido-Me3N-7-CB10H12的定量产率，这是由于叔丁基团的交换。nido-tBuMeHN-7-CB10H12的11B NMR谱作为pH的函数被探索，展示了与nido-tBuMeN-7-CB10H12⁻的交换。B10H14与CyNC的反应生成nido-CyH2N-7-CB10H12，该化合物在THF中与Na2CO3和(MeO)2SO2甲基化，得到nido-CyMe2N-7-CB10H12。nido-Me3N-7-CB10H12和nido-CyMe2N-7-CB10H12的去质子化分别得到Na[nido-Me3N-7-CB10H11]和Na[nido-CyMe2N-7-CB10H11]。这两种三烷基（氨基）卡博烯可以转化为Na[nido-CB10H13]，后者是低配位阴离子closo-CB11H12⁻的前体。通过单晶X射线衍射确定的nido-tBuMeHN-7-CB10H12和nido-CyMe2N-7-CB10H12的分子结构被报道。
• Alkyne coupling at a rhenium–monocarborane substrate: synthesis of Re,B-η2:σ-butadienyl complexes
  作者：Shaowu Du、Jason A. Kautz、Thomas D. McGrath、F. Gordon A. Stone

  DOI：10.1039/b510026g

  日期：——

  12 in tetrahydrofuran (THF) with LiBun (3 equiv) and then [ReBr(CO)3(THF)2] gives the rhenacarborane dianion [1-NHBut-2,2,2-(CO)3-closo-2,1-ReCB10H10]2−, isolated as the bis-[N(PPh3)2]+ salt (4). Iodine oxidation of this ReI intermediate gives the ReIII complex [1,2-µ-NHBut-2,2,2-(CO)3-closo-2,1-ReCB10H10] 6 in which the carborane functions formally as an 8-electron (6π + 2σ) donor. Reaction of 6 with

  7-NH 2 Bu t - nido -7-CB 10 H 12的处理。四氢呋喃（THF）与礼部Ñ （3当量），然后[ReBr（CO）3（THF）2 ]给出rhenacarborane二价阴离子[1-NHBu吨-2,2,2-（CO）3 -闭合碳-2,1- ReCB 10 H 10 ] 2-作为双-[N（PPh 3）2 ] +盐（4）分离。碘氧化作用这个重新的我中间给出了Re III复杂[1,2-μ-NHBu吨-2,2,2-（CO）3 -闭合碳-2,1-ReCB 10 ħ 10 ] 6，其中碳硼烷正式起8电子（6π+2σ）供体的作用。反应6与配体L的我的存在3 NO给出取代的产物[1,2-μ-NHBu吨-2,2-（CO）2 -2-L-闭合碳-2,1-ReCB 10 ħ 10 ] [L = PPH 3 （图7a），CNXyl（7B ;的Xyl = C 6 H ^ 3我2 -2,6），或卜吨ç
• Alkyne coupling in rhenacarbaborane chemistry. Structure of [1,2-µ-NHBut-2,2-(CO)2-3,2-σ:η2-{C(CHBut)–CHCHBut}-closo-2,1-ReCB10H9]
  作者：Shaowu Du、Jason A. Kautz、Thomas D. McGrath、F. Gordon A. Stone

  DOI：10.1039/b201772p

  日期：2002.4.19

  The butadienyl moiety in the title compound is bound to both cage-boron and rhenium vertices, and arises from coupling of two alkyne molecules at the rhenium centre, unprecedented in metallacarbaborane chemistry.

  标题化合物中的丁二烯分子与笼硼和铼的顶点都结合在一起，是两个炔分子在铼中心耦合产生的，这在金属硼烷化学中是前所未有的。
• Synthesis of Charge-Compensated Octacarbonyltriruthenium Monocarbollide Complexes
  作者：Vyacheslav N. Lebedev、Donald F. Mullica、Eric L. Sappenfield、F. Gordon A. Stone

  DOI：10.1021/om950725p

  日期：1996.3.19

  transoid to Ru(1), while the third Ru atom is terminally attached to three CO molecules. The Ru(2)−Ru(3) connectivity is bridged by a hydrido ligand, and in addition both of these metal atoms are linked to the CB10 framework through boron atoms in the β-sites of the CBBBB ring coordinated to Ru(1). Atom Ru(2) forms a three-center, two-electron B−H⇀Ru bond, while atom Ru(3) forms an Ru−B σ-bond, with the

  电荷补偿monocarbon碳硼烷巢-7-NR 3 -7-CB 10 ħ 12，以[Ru反应3（CO）12 ]中在回流温度下的甲苯，得到三钌配合物的[Ru 3（CO）8（η 5 - 7-NR 3 -7-CB 10 ħ 10）] [NR 3 = NME 3（1A），NH 2卜吨（1B），和NME 2卜吨（1C）。1a的分子结构通过X射线晶体学已经建立。金属原子形成基本上等腰的三角形。一个Ru原子带有两个末端CO基团和以五足配位的nido -7-NMe 3 -7-CB 10 H 10笼。相对于CB BB B环中的碳，β位中的两个硼原子与其他两个Ru原子形成外多面体三中心，两个电子的B-H⇀Ru键。这些金属原子还带有三个基本上末端连接的CO配体。的治疗1A与PPH 3在甲苯中，得到的混合物，[Ru中的柱色谱法后3（μ-H）（μ 3 -σ：η 5 -7- NME3 -7-CB 10 ħ 9）（CO）7（PPH
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.2, 7.4.1.2, page 239 - 241
  作者：

  DOI：——

  日期：——