Cr[N(SiMe₃)₂]₂(THF)₂ | 73208-55-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: Cr[N(SiMe₃)₂]₂(THF)₂
• 英文别名: Bis(trimethylsilyl)azanide;chromium(2+);oxolane
• CAS: 73208-55-6
• 化学式: C₂₀H₅₂CrN₂O₂Si₄
• 分子量: 516.983
• InChiKey: BROFYXVRJRYLKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.65
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Cr[N(SiMe₃)₂]₂(THF)₂ 、 过氧化二异丙苯 以 正戊烷 为溶剂， 以25%的产率得到[Cr(bis(trimethylsilyl)amido)(OCMe2Ph)2]
  参考文献：
  名称：

  铬（III）和铬（IV）双（三甲基甲硅烷基）酰胺基络合物作为乙烯聚合催化剂。

  摘要：

  Cr [N（SiMe（3））（2）]（2）（THF）（2）用碘和二枯基过氧化物氧化产生四面体Cr（iv）Cr [N（SiMe（3））（2）]（ 2）I（2）和三角形平面Cr（iii）Cr [N（SiMe（3））（2）]（OCMe（2）Ph）（2）；两种配合物均已通过单晶X射线衍射进行了表征，并且均具有与烷基铝助催化剂进行乙烯聚合的活性。

  DOI：

  10.1039/b412584c
• 作为产物：
  描述：

  四氢呋喃 、 CrCl₂(THF) 、 sodium hexamethyldisilazane 以 四氢呋喃 为溶剂， 以71%的产率得到Cr[N(SiMe₃)₂]₂(THF)₂
  参考文献：
  名称：

  Aryl-Containing Chelates and Amine Debenzylation to Afford 1,3-Di-2-pyridyl-2-azaallyl (smif): Structures of {κ-C,N,N^py₂-(2-pyridylmethyl)₂N(CH₂(4-^tBu-phenyl-2-yl))}FeBr and (smif)CrN(TMS)₂

  摘要：

  Aryl-bromide ligand precursors have been prepared with the potential to afford tetradentate chelates (2-pyridylmethyl)(3-x)N(CH2-2-Aryl)(x)(x = 1, 2) containing metal-aryl linkages that promise to impart stronger fields about first row transition metals. Oxidative addition to Ni(COD)(2) afforded two diamagnetic Ni(II) complexes, (kappa-C,N,N-py-(2-pyridylmethyl)N(CH2(4-Bu-t-phenyl-2-yl))(CH2(4-Bu-t-phenyl-2-Br))}NiBr (1-Ni) and {(kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}NiBr (2-Ni) in 96% and 67% yield, respectively. Extending these synthetic efforts to iron provided {kappa-C,N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-yl))}FeBr (2-Fe, X-ray) in 91% yield via reduction of an adduct, {kappa-N,N-2(py)-(2-pyridylmethyl)(2)N(CH2(4-Bu-t-phenyl-2-Br))}FeBr2 (3-Fe). 5-Coordinate 2-Fe possessed a pseudo-tbp structure, and SQUID magnetometry showed it to be S = 2 with significant zero field splitting (ZFS). 2Fe was initially prepared via oxidative addition to Fe{N(TMS)(2))(2)(THF) upon disproportionation to "Fe(0)" and 2 Fe{N(TMS)(2)}(3), but when this approach was attempted with Cr{N(TMS)(2)}(2)(THF)(2), the azaallyl complex {kappa-N,N-2(py)-1,3-dipyridyl-2-azaallyl}CrN(TMS)(2) ((smif)CrN(TMS)(2), 4-Cr, X-ray), formed instead (>50%) via amine debenzylation. An alternative route consisting of addition of 1,3-di-2-pyridyl-2-azapropene to Cr{N(TMS)(2)}(2)(THF)(2) afforded 4-Cr in 74% yield. Pseudo-square planar 4-Cr was also S = 2 (SQUID) with marked ZFS. The dipyridylazaallyl ligand "smif" imparts a remarkable optical density to 4-Cr via intraligand bands at 675 nm (epsilon similar to 15 000 M(-1)cm(-1)) and 396 nm (epsilon similar to 27 000 M(-1)cm(-1)). The effective fields of the chelate complexes are discussed, and a comparison of smif to isoelectronic NHC ligands is given.

  DOI：

  10.1021/ic901329z

文献信息

• Isocyanide and Phosphine Oxide Coordination in Binuclear Chromium Pacman Complexes
  作者：Charlotte J. Stevens、Gary S. Nichol、Polly L. Arnold、Jason B. Love

  DOI：10.1021/om4009313

  日期：2013.12.9

  The new binuclear chromium Pacman complex [Cr2(L)] of the Schiff base pyrrole macrocycle H4L has been synthesized and structurally characterized. Addition of isocyanide, C≡NR (R = xylyl, tBu), or triphenylphosphine oxide donors to [Cr2(L)] gives contrasting chemistry with the formation of the new coordination compounds [Cr2(μ-CNR)(L)], in which the isocyanides bridge the two Cr(II) centers, and [Cr2(OPPh3)2(L)]

  希夫碱吡咯大环 H 4 L的新型双核铬 Pacman 配合物 [Cr 2 (L)]已合成并进行结构表征。将异氰化物、C≡NR（R = 二甲苯基，t Bu）或三苯基氧化膦供体添加到 [Cr 2 (L)] 中，会产生与新配位化合物 [Cr 2 (μ-CNR)(L)形成对比的化学反应] ]，其中异氰化物桥接两个 Cr(II) 中心，和 [Cr 2 (OPPh 3 ) 2 (L)]，一种 Cr(II) 氧化膦加合物，配体是裂缝的外源性。
• On the Synthesis and Reduction of Trigonal Halido Bis(silylamido) Metalates of Chromium to Cobalt
  作者：Ruth Weller、Lena Völlinger、C. Gunnar Werncke

  DOI：10.1002/ejic.202100716

  日期：2021.11.15

  The general synthesis of trigonal bromido metal(II) silylamides via adduct formation with tetrabutylammonium bromide or oxidation of linear metal(I) complexes as well as their reduction is presented. The adduct formation is also extended to benzyl potassium yielding benzyl manganese and cobalt complexes.

  介绍了通过与四丁基溴化铵形成加合物或线性金属 (I) 配合物的氧化以及它们的还原来合成三方溴化金属 (II) 甲硅烷基酰胺。加合物的形成也扩展到苄基钾，产生苄基锰和钴配合物。
• Direct Synthesis of Ligand-Based Radicals by the Addition of Bipyridine to Chromium(II) Compounds
  作者：Wen Zhou、Addison N. Desnoyer、James A. Bailey、Brian O. Patrick、Kevin M. Smith

  DOI：10.1021/ic302590g

  日期：2013.3.4

  The reaction of 2,2′-bipyridine (bpy) with monomeric chromium(II) precursors was used to prepare the S = 1 complexes Cr(tBu-acac)2(bpy) (1) and (η5-Cp)(η1-Cp)Cr(bpy) (3), as well as the S = 2 compound Cr[N(SiMe3)2]2(bpy) (4). The crystallographically determined bond lengths indicate that the bpy ligands in 1 and 3 are best regarded as radical anions, while 4 shows no structural evidence for electron

  2,2'-联吡啶（BPY）与单体铬（II）前体的反应物用于制备小号= 1个复合铬（TBU-ACAC）2（联吡啶）（1）和（η 5 -Cp）（η 1 -Cp）Cr（bpy）（3）以及S = 2化合物Cr [N（SiMe 3）2 ] 2（bpy）（4）。晶体学上确定的键长表明，最好将1和3中的bpy配体视为自由基阴离子，而4则没有显示出电子从Cr II转移至中性bpy配体的结构证据。
• Uniaxial magnetic anisotropy of square-planar chromium(<scp>ii</scp>) complexes revealed by magnetic and HF-EPR studies
  作者：Yi-Fei Deng、Tian Han、Zhenxing Wang、Zhongwen Ouyang、Bing Yin、Zhiping Zheng、J. Krzystek、Yan-Zhen Zheng

  DOI：10.1039/c5cc07025b

  日期：——

  Two mononuclear square-planar Cr(II) complexes are reported, exhibiting field-induced slow magnetic relaxation. The axial zero-field splitting parameter was unambiguously determined by both high-frequency/field electron paramagnetic resonance (HF-EPR) technique and magnetic...

  报道了两个单核方平面Cr（II）配合物，表现出场诱导的慢磁弛豫。轴向零场分裂参数是通过高频/场电子顺磁共振（HF-EPR）技术和磁...
• ‘Pincer’ dicarbene complexes of some early transition metals and uranium
  作者：David Pugh、Joseph A. Wright、Sandra Freeman、Andreas A. Danopoulos

  DOI：10.1039/b512133g

  日期：——

  6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium

  [（CNC）MX（n）（thf）（m）]与“夹子” 2,6-双（咪唑基亚基）吡啶的络合物，（CNC）= 2,6-双（芳基咪唑-2-亚基）吡啶，芳基= 2,6-Pr（i）2C6H3，M = V，X = Cl，n = 2，m = 1 1a; M = Cr，X = Cl，n = 2，m = 0，2a，X = Br，2b；M = Mn，X = Br，n = 2，m = 0，3; M = Nb，X = Cl，n = 3，m = 0，4；和M = U，X = Cl，n = 4，m = 0，5，通过（a）用游离的（CNC）取代不稳定的tmed（1a），thf（2a，3，5）或dme（4）合成）或通过（b）双咪唑鎓盐（CH-N-CH）Br2与Cr [N（SiMe3）2] 2（thf）2}反应，然后进行胺消除（2b）。尝试用格利雅（Grignard）或烷基锂将1a，2、3a和4烷基化，得到了难处理的混合物