potassium naphthalenide

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: potassium naphthalenide
• 英文别名: potassium naphthalide；potassium naphthalene；Naphthalene potassium
• 化学式: C₁₀H₈K
• 分子量: 167.272
• InChiKey: IJJSYKQZFFGIEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.46
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  potassium naphthalenide 以 四氢呋喃 为溶剂， 生成 K{Co(2,6-Me2C6H3NC)4}
  参考文献：
  名称：

  Synthesis and Structural Characterization of [Co{CN(2,6-C6H3Me2)}4]-, the First Transition Metal Isonitrilate

  摘要：

  The homoleptic Co(-I) isonitrile complex [Co(CNPh*)(4)](-) (1(-), Ph* = 2,6-C(6)H(3)Me(2)), the first example of an isonitrilate complex, can be prepared by ethylene substitution within the Co(-I) complex [CO(C2H4)(4)](-) or by potassium naphthalenide (K(Nap)) reduction of Co(O), Co(I), and Co(II) substrates. Reductions of the isonitrile-containing precursors [Co(CNPh*)(4)I-2] (3) and [Co(CNPh*)(5)](+) (4(+)) proceed via [Co-2(CNPh*)(8)] (2), which is then reduced further to 1(-). Complex 1(-) can be prepared in one pot by K(Nap) reduction of cobaltocene followed by addition of CNPh* or by potassium reduction of a mixture of CoI2 and CNPh* to give 2, which is then further reduced to 1(-). The anion 1(-) can be isolated as K+, [K(DME)](+), [K(crypt-2,2,2)](+), and [K(18-C-6)](+) salts and has been characterized spectroscopically and analytically. Oxidation of 1(-) gives 2, which is the only observable product from the reaction of 1(-) with many simple electrophiles. The only electrophilic adduct of 1(-) isolated to date is [Co(CNPh*)(4)(SnPh(3))] (5), the product of reaction with Ph(3)SnCl. Single-crystal X-ray diffraction has confirmed that [K(DME)]1 contains discrete, approximately tetrahedral cobalt anions held together as loose dimers through interactions with the [K(DME)](+) counterions (space group , with a = 11.160(2) Angstrom, b = 14.204(3) Angstrom, c = 14.339(3) Angstrom, alpha = 102.91(1)degrees, beta = 11.88(1)degrees, gamma = 102.78(1)degrees, D-c = 1.223 g/mL, Z = 2, and R(F) = 5.93%). Crystallography has also established that 2 is a dimer with two bridging isonitrile groups (space group , with a = 12.239(4) Angstrom, b = 13.985(4) Angstrom, c = 21.609(6) Angstrom, alpha = 98.87(2)degrees, beta = 99.19(2)degrees, gamma = 112.72(2)degrees, D-c = 1.185 g/mL, Z = 2, and R(F) = 6.10%), and examination of molecular parameters for 1(-) and 2 suggest that increased back-donation of electron density from the metal results in significant lengthening of the C=N triple bond in 1(-) but has no consistent effect on the CNC bend angles of the ligands. Decreases in the CNC angles correlate instead with close approaches between the carbon atoms of the ligands and the [K(DME)](+) counterions, which are also responsible for the major distortions of the metal geometry away from that of an ideal tetrahedron.

  DOI：

  10.1021/ja00098a017
• 作为产物：
  描述：

  萘 在 氢化钾 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以65%的产率得到potassium naphthalenide
  参考文献：
  名称：

  118年后，将两种常见的自由基阴离子还原剂分离为简单，稳定的固体。

  摘要：

  两种常见的自由基阴离子还原剂，二苯甲酮酮基钾（K（Ph（2）CO））和萘二甲酸钾（K（2）（C（10）H（8））（2）（THF））进行了表征首次以无溶剂形式或溶剂含量较低的形式，以精确的化学计量量将其用作制备型氧化还原化学中的纯固体反应物。

  DOI：

  10.1039/b815272a
• 作为试剂：
  描述：

  二苯基氯化膦 在 正丁基锂 、 potassium naphthalenide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 25.0h， 生成 potassium diphenylphosphine
  参考文献：
  名称：

  Extremely bulky secondary phosphinoamines as substituents for sterically hindered aminosilanes

  摘要：

  一系列具有磷胺功能的极为庞大的二级胺的合成被描述为Ar†(PR2)NH（Ar†= C6H2{C(H)Ph2}2Pr-i-2,6,4; R = Ph, NEt2, NPr-i2）。使用n-BuLi或KH去质子化会产生相应的碱金属酰胺。与一系列氯硅烷反应可获得带有极为庞大氨基取代基的单分子化合物，通过盐消除作用实现。

  DOI：

  10.1039/c5dt02504d

文献信息

• One- and two-electron reduction of a chromium(0) alkyne complex and isolation of the chromium(1-) product
  作者：Donald J. Wink、James R. Fox、N. John Cooper

  DOI：10.1021/ja00303a041

  日期：1985.8

  Preparation et reduction de [Cr(C 4 Ph 4 )(C 2 Ph 2 )(CO) 2 ] (1). Obtention d'un radical (1-) remarquablement stable mais il peut etre reduit en 1 2− sans perte de coordinat

  [Cr(C 4 Ph 4 )(C 2 Ph 2 )(CO) 2 ] (1) 的制备和还原。Obtention d'un Radial (1-) remarquablement stable mais il peut etre reduit en 1 2− sans perte de coordinat
• Highly reduced organometallics. 33. Carbonyl hydrides of titanium and corresponding carbonyltitanates
  作者：John E. Ellis、Beatrice Kelsey Stein、Scott R. Frerichs

  DOI：10.1021/ja00063a027

  日期：1993.5

  provided new zerovalent titanium carbonyls of the general formula [(C 5 R 5 )Ti(CO) 3 (PR 3 )] - . Disubstituted phosphine derivatives of the formula [(C 5 R 5 )Ti(CO) 2 (dmpe)] - were obtained by the alkali metal naphthalenide promoted reductive cleavages of titanocene dicarbonyls (C 5 R 5 ) 2 Ti(CO) 2 (R=H, Me) in the presence of dmpe, i.e., 1,2-bis(dimethylphosphino)ethane.

  [(C 5 R 5 )Ti(CO) 4 ] - (R=H, Me) 与有机膦的光促进取代反应首次被研究，并提供了通式 [(C 5 R 5 )Ti(CO) 3 (PR 3 )] - 。式[(C 5 R 5 )Ti(CO) 2 (dmpe)]的二取代膦衍生物是通过碱金属萘化物促进二茂钛二羰基化合物(C 5 R 5 ) 2 Ti(CO) 2 (R =H，Me)在dmpe，即1,2-双(二甲基膦基)乙烷的存在下。
• A reactive iron napthalene complex provides convenient access to the Cp*Fe− synthon (Cp*C5Me5)
  作者：Robert Wolf、Eva-Maria Schnöckelborg

  DOI：10.1039/b926986j

  日期：——

  The complex [K(18-crown-6)Cp*Fe(η4-C10H8)}] (1), which is readily available from easily accessible starting materials, represents a new, synthetically useful Cp*Fe− equivalent.

  复合物[K(18-crown-6)Cp*Fe(δ-4-C10H8)}]（1）很容易从容易获得的起始材料中获得，是一种新的、合成上有用的 Cp*Feâ 等效物。
• Synthesis, derivatization, and structural characterization of [Mn(CNC6H3Me2-2,6)5] −, a five-coordinate isonitrilate complex containing Mn−I
  作者：Tracy L. Utz、Patricia A. Leach、Steven J. Geib、N. John Cooper

  DOI：10.1039/a700089h

  日期：——

  Naphthalenide reduction of [Mn(CNC 6 H 3 Me 2 -2,6) 5 Cl] forms solutions of trigonal-bipyramidal [Mn(CNC 6 H 3 Me 2 -2,6) 5 ] - , as established by an X-ray diffraction study of a [K(18-C-6)(dme)] + salt and derivatization with SnClPh 3 to give [Mn(CNC 6 H 3 Me 2 -2,6) 5 (SnPh 3 )].

  萘还原 [锰(数控 6 H 3 我 2 -2,6) 5 Cl]形式 三方双锥解 [锰(数控 6 H 3 我 2 -2,6) 5 ] - ，通过 X 射线衍射研究确定 [K(18-C-6)(dme)] + 盐和衍生化 氯化亚锡 3 给予 [锰(数控 6 H 3 我 2 -2,6) 5 (SnPh 3 )]。
• Bis(cyclopentadienyl)technetium(III)chlorid und Tris(cyclopentadienyl)technetium(III), neue metallorganische Verbindungen des dreiwertigen Technetiums
  作者：Christos Apostolidis、Basil Kanellakopulos、Ralph Maier、Jean Rebizant、Manfred L. Ziegler

  DOI：10.1016/0022-328x(90)85473-c

  日期：1990.10

  Technetium tetrachloride reacts with potassium cyclopentadienide in tetrahydrofuran to give the diamagnetic, air-stable (C5H5)2TcCl (1). Single crystal X-ray diffraction analysis shows a short ring-metal distance of 187.7(5) pm, which is comparable with the corresponding distance in nickelocene, indicating high covalency. Reaction of the compound with KC5H5 gives the red (C5H5)3Tc (4), in which one

  四氯化与环戊二烯化钾在四氢呋喃中反应，生成抗磁性，空气稳定的（C 5 H 5）2 TcCl（1）。单晶X射线衍射分析显示，较短的环金属距离为187.7（5）pm，与镍全新世的相应距离相当，表明共价较高。化合物与KC 5 H 5反应得到红色（C 5 H 5）3 Tc（4），其中一个环戊二烯基环与σ键相连。后一种化合物的质谱研究表明存在（C 5 H 5）4 Tc。讨论了（C 5 H 5）2 TcCl的反应性。