K(Priso) | 1119723-34-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: K(Priso)
• 英文别名: potassium(N(2,6-iPr2C6H3))2C(N(iPr2))；K((2,6-diisopropylphenyl)N)2CNiPr2)
• CAS: 1119723-34-0
• 化学式: C₃₁H₄₈N₃*K
• 分子量: 501.841
• InChiKey: NHWHPBUWZMUCTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.0
• 重原子数：
  35.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  29.7
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  K(Priso) 、 iron(II) bromide 以 四氢呋喃 为溶剂， 反应 36.0h， 以79%的产率得到
  参考文献：
  名称：

  Donor Properties of a New Class of Guanidinate Ligands Possessing Ketimine Backbones: A Comparative Study Using Iron

  摘要：

  Addition of 1 equiv of LiN=(CBu2)-Bu-t or LiN=Ad (Ad = 2-adamantyl) to the aryl carbodiimide C(NDipp)(2) (Dipp = 2,6-diisopropylphenyl) readily generates the lithium ketimine-guanidinates Li(THF)(2)[(X)C(NDipp)(2)] (X = N=(CBu2)-Bu-t (1-Bu-t), N=-Ad (1-Ad)) in excellent yields. These new ligands can be readily metalated with iron to give the N,N'-bidentate chelates [{(X)C(NDipp)(2)}-FeBr](2) (X = N=(CBu2)-Bu-t (5-Bu-t), N=Ad (5-Ad)), in which the ketimines behave as noncoordinating backbone subst:ituents. In an effort to understand the potential electronic contributions of the ketimine group to the ligand architecture, a thorough structural and electronic study was conducted comparing the features and properties of 5-Bu-t and 5-Ad to their guanidinate and amidinate analogues [I(X) C(NDipp)(2)}FeBr](2) (X = (Pr2N)-Pr-i (6), Bu-t (7)). Solid-state structural analyses indicate little electronic contribution from the N-ketimine nitrogen atom, while solution-phase electronic absorption spectra of 5-Bu-t and 5-Ad are qualitatively similar to the amidinate complex 7. Yet, electrochemical measurements do show the donor properties of the ketimineguanidinate in 5-Bu-t to be intermediate between its guanidinate and amidinate counterparts in 6 and 7. Preliminary reactivity studies also show that the reduction chemistry of 5-Bu-t diverges significantly from that of 6 and 7. Treatment of 5-Bu-t with excess magnesium or 1 equiv of KC8 leads to the formation of the Fe(I)-Fe(I) complex [mu-((Bu2C)-Bu-t=N)C(NDipp)(2)}(2)Fe-2] (11), which possesses an exceedingly short Fe=Fe bond (2.1516(5) angstrom), while neither 6 nor 7 forms dinuclear complexes upon reduction. This result demonstrates that ketitine-guanidinates do not simply behave as amidinate variants but can contribute to distinctive metal chemistry of their own.

  DOI：

  10.1021/acs.inorgchem.5b01815
• 作为产物：
  描述：

  2,3-bis(2,6-diisopropylphenyl)-1,1-diisopropylguanidine 在 双(三甲基硅烷基)氨基钾 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以86%的产率得到K(Priso)
  参考文献：
  名称：

  Synthesis and characterisation of bulky guanidines and phosphaguanidines: precursors for low oxidation state metallacycles

  摘要：

  碱金属酰胺或磷化物与大体积碳二亚胺 ArNCNAr（Ar = C6H3Pri2-2,6）反应，然后进行水性加 工，得到了几种胍类化合物 ArNC(NR2)N(H)Ar（R = 环己基 (GisoH) 或 Pri (PrisoH)）；NR2=顺式-NC5H8Me2-2,6（PipisoH））、一种双官能胍，{ArNCN(H)Ar}2{μ-N(C2H4)2N}（Pip(GisoH)2）和两种磷胍，ArNC(PR2)N(H)Ar（R=环己基（CyP-GisoH）或 Ph（PhP-GisoH））。我们还通过其他方法制备了一种非常笨重的胍类化合物 ArNC{N(Ar)SiMe3}N(H)Ar (ArSi-Giso)，以及一种芳基偶联双官能胍类化合物 {ArN(H)C(NPri2)NC6H2Pri2-2,6-}2 (PrisoH)2。所有化合物都经过了晶体学表征，并显示在固态下存在多种异构体。这些异构体似乎在溶液中基本保持不变。GisoH 与 BunLi 在己烷或四氢呋喃中发生去质子化反应，分别生成了具有晶体学特征的二聚体和单体复合物，即 [Li{Li(κ2-N,N′-Giso)2}] 和 [Li(THF)(η1-N,η3-Ar-Giso)]。PrisoH 和 Pip(GisoH)2 与 K[N(SiMe3)2] 发生去质子化反应后，分别得到非溶解聚合物 [{K(η1-N,η6-Ar-Priso)}∞] 和溶解复合物 [{K(THF)2}{Pip(Giso)2}{K(THF)3}]。

  DOI：

  10.1039/b809120j

文献信息

• Low coordinate lanthanide(ii) complexes supported by bulky guanidinato and amidinato ligands
  作者：Dennis Heitmann、Cameron Jones、David P. Mills、Andreas Stasch

  DOI：10.1039/b924367d

  日期：——

  the closely related complex, [(κ2-N,N′-Priso)Yb(THF)(μ-I)}2], the ytterbium atoms are κ2-N,N′-chelated by the guanidinate ligand. The facility of the planar four-coordinate complex, [Sm(Giso)2], to act as a one-electron reducing agent towards a variety of unsaturated substrates has also been explored. The complex has been shown to selectively reductively couple CS2, via a C–S bond formation, to give

  编写一系列均四，四坐标 镧系元素（II）络合物[Ln（Priso）2 ]（Ln =m， 欧盟 或者 b）合并笨重 胍盐配体Priso -（[（ArN ）2 CNPr i 2] -，氩气 = 2,6-二异丙基苯基）进行了说明。X射线晶体学显示该配合物是同构的，并且在四面体和平面之间的中间表现出配位几何形状。复合物的几何形状和与笨重的系统之间的比较，[LN（Giso）2 ]（Giso - = [（ArN ）2 CNCy 2] -，半胱氨酸=环己基）。尝试准备受阻较小的人mid 配合物，[Ln（皮索）2]（皮索- = [（ARN）2 CBU吨] - ），没有成功，但确实引起的杂配体络合物，[（κ 1 -N，η 6 -Piso）的Sm（THF）（μ-I）2 SM（κ 1 -N，η 6 -Piso）]。而该络合物中的mid酰胺配体则螯合了钐中心在κ 1 -N，η 6 -Ar-方式，在密切相关的复杂的，[（κ
• Amidinato- and Guanidinato-Cobalt(I) Complexes: Characterization of Exceptionally Short Co-Co Interactions
  作者：Cameron Jones、Christian Schulten、Richard P. Rose、Andreas Stasch、Simon Aldridge、William D. Woodul、Keith S. Murray、Boujemaa Moubaraki、Marcin Brynda、Giovanni La Macchia、Laura Gagliardi

  DOI：10.1002/anie.200900780

  日期：2009.9.21

  CoCo loco! Ligand‐bridged dimers (see picture) with the shortest known Co–Co interactions are the first amidinato and guanidinato cobalt(I) complexes. The nature of the interactions has been probed by magnetic and theoretical investigations, and has been shown to be multiconfigurational. Preliminary reactivity studies of the complexes have also been carried out.

  可可机车！已知Co-Co相互作用最短的配体桥联二聚体（见图）是第一个a基和胍基钴（I）配合物。相互作用的性质已通过磁性和理论研究探究，并已证明是多构型的。配合物的初步反应性研究也已经进行。
• Stabilisation of carbonyl free amidinato-manganese(<scp>ii</scp>) hydride complexes: “masked” sources of manganese(<scp>i</scp>) in organometallic synthesis
  作者：Lea Fohlmeister、Cameron Jones

  DOI：10.1039/c5dt04504e

  日期：——

  η3-arene-Piso)Mn(μ-H)2}2] and the isomorphous manganese(I) complex, [(N-,η3-arene-Piso)Mn}2], toward CO, O2 and N2O was carried out. Reactions with the manganese(I) and manganese(II) species gave identical results, namely the formation of the manganese(I) carbonyl complex, [(κ2-N,N′-Piso)Mn(CO)4] (reactions with CO), and the manganese(III)-μ-oxo complex, [(κ2-N,N′-Piso)Mn(μ-O)}2] (reactions with O2

  所述amidinato锰（的反应II），溴化络合物，[（κ 2 - Ñ，Ñ '-Piso）的Mn（μ-溴）} 3（THF）2 ]（皮索= [（DIPN）2 CBU吨] -，DIP = 2,6-二异丙基）中，用K [BHET 3 ]得到的第一示例的结构认证amidinato锰（II）氢化物络合物，[（ñ - ，η 3 -arene-皮索）的Mn（μ- H）2 } 2 ]，通过涉及改变ate酰胺配位模式的过程。处理体积较大的前体复合物[（Piso''）Mn（μ-Br）}n ]（Piso''= [（Dip''N） 2 CBu t ] -，Dip''= C 6 H 2 Pr i 2（CPh 3）-2,6,4），用K [BHEt 3 ]做不会导致可分离的氢化锰配合物，但会与镁（I）配合物[（ Mes Nacnac）Mg} 2 ]（ Mes Nacnac = [（MesNCMe） 2 CH] -，Mes
• Flexible coordination of bulky amidinates and guanidinates towards rhodium(i): conversion of kinetic to thermodymanic isomers
  作者：Cameron Jones、David P. Mills、Andreas Stasch

  DOI：10.1039/b806542j

  日期：——

  Reactions of the bulky amidinate and guanidinate salts K[(ArN)2CR] (R = But, NPri2 or N(C6H11)2; Ar = 2,6-diisopropylphenyl) with [RhCl(η4-COD)}2] (COD = 1,5-cyclooctadiene) lead to KCl elimination and the formation of the complexes, [Rh(η5-ArN)(ArN)CR}(COD)], in which the anionic ligand coordinates the rhodium centre in an unprecedented η5-cyclohexadienyl mode. The thermal conversions of these complexes to their N,N′-chelated isomers, [Rhκ2-N,N′-(ArN)2CR}(COD)], were carried out and the kinetics of these processes have been shown to be first order. The rates of the isomerisations are inversely proportional to the size of the amidinate or guanidinate backbone substituent. Analogies between the ligating properties of the bulky amidinates and guanidinates used in the study, and those of β-diketiminates are discussed.

  笨重的脒酸盐和胍酸盐 K[(ArN)2CR]（R = But、NPri2 或 N(C6H11)2；Ar=2,6-二异丙基苯基）与[RhCl(η4-COD)}2]（COD=1,5-环辛二烯）的反应导致 KCl 消解并形成[Rh(η5-ArN)(ArN)CR}(COD)]配合物，其中阴离子配体以前所未有的 η5-环己二烯模式配位铑中心。研究人员进行了这些配合物向其 N,N′-螯合异构体[Rhκ2-N,N′-(ArN)2CR}(COD)]的热转化，结果表明这些过程的动力学是一阶的。异构化的速率与脒基或胍基骨架取代基的大小成反比。研究中使用的大块脒基和胍基的连接特性与 β-二酮亚胺的连接特性进行了类比讨论。