[(N(SiMe2CH2P(t)Bu2)2)NiCl] | 1006375-75-2

• 英文名称: [(N(SiMe2CH2P(t)Bu2)2)NiCl]
• 英文别名: NiCl(N(SiMe2CH2P(tBu)2)2)；((tBu2PCH2SiMe2)2N)NiCl；[(tBu2PCH2SiMe2)N(tBu2PCH2SiMe2)]NiCl；[η2-(t-Bu2PCH2SiMe2)2N]NiCl
• CAS: 1006375-75-2
• 化学式: C₂₂H₅₂ClNNiP₂Si₂
• 分子量: 542.923
• InChiKey: PZVNYRJHQRLWFT-UHFFFAOYSA-M

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：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(N(SiMe2CH2P(t)Bu2)2)NiCl] 以 苯 为溶剂， 生成 NiH(O(SiMe₂CH₂P(tBu)2)2)(cyanate-N)
  参考文献：
  名称：

  Unusual selectivity of a (pincer)Ni-hydride reacting with CO2

  摘要：

  (PNP)NiH（其中 PNP 为 (tBu2PCH2SiMe2)2N−1）与 CO2 在 25 °C 下发生数小时反应，形成 (POP)NiH(NCO)，其中涉及初始酰胺氮和一个的转位氧气CO2。

  DOI：

  10.1039/b822677f
• 作为产物：
  描述：

  六氯乙烷 、 ((t-Bu2PCH2SiMe2)2N)Ni 以 氘代苯 为溶剂， 生成 [(N(SiMe2CH2P(t)Bu2)2)NiCl]
  参考文献：
  名称：

  Evaluating the reducing power of 3-coordinate T-shaped NiI

  摘要：

  The reactivity of (PNP)Ni-I, where PNP = ((Bu2PCH2SiMe2)-Bu-t)(2)N, with oxidants was evaluated. Towards the nitroxyl TEMPO, a 1:1 adduct is formed which was shown to have eta(2)-TEMPO bound through both N and O, with the consequence that one P of the PNP ligand is displaced, leaving the pincer ligand bidentate to Ni-II. DFT calculations show that the bidentate character of TEMPO is due to steric clash between Bu-t and TEMPO ring methyl groups. Reaction of (PNP)Ni with I-2, Br-2, C2Cl6 and even CH2Cl2 all yield (PNP)(NiX)-X-II, but never (PNP)(NiX2)-X-III. Excess Br-2 instead oxidizes one phosphorus, yielding the zwitterion [((BrBu2PCH2SiMe2)-Bu-t)N((SiMe2CH2PBu2)-Bu-t)]NiBr2, whose structure is determined. DFT calculation of the species (PNP)Ni-III(Br)(2) yields reaction thermodynamics which show the reason for its absence, and also shows the low BDE of its Ni-Br bond. (PNP)Ni slowly catalyzes the polymerization of HCCR (R = H or Ph), but gives no detectable conversion to a new alkyne-derived nickel complex. (c) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.12.059

文献信息

• Three-Coordinate Ni^II: Tracing the Origin of an Unusual, Facile Si−C(sp³) Bond Cleavage in [(^<i>t</i>Bu₂PCH₂SiMe₂)₂N]Ni⁺
  作者：Benjamin C. Fullmer、Hongjun Fan、Maren Pink、John C. Huffman、Nikolay P. Tsvetkov、Kenneth G. Caulton

  DOI：10.1021/ja108426f

  日期：2011.3.2

  instead ((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)OTf)Ni(CH(2)P(t)Bu(2)). Abstraction of F(-) from (PNP)NiF by even a catalytic amount of BF(3) causes rearrangement of the (transient) (PNP)Ni(+) to analogous ring-opened [((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)F)]Ni(CH(2)P(t)Bu(2)). Abstraction of Cl(-) from (PNP)NiCl with NaB(C(6)H(3)(CF(3))(2))(4) in CH(2)Cl(2) or C(6)H(5)F gives (PNP)NiB(C(6)H(3)(CF(3))(2))(4), the key

  所有试图合成 (PNP)Ni(OTf) 的尝试都形成 ((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)OTf)Ni(CH(2)P(t)Bu(2)) . 通过甚至催化量的 BF(3) 从 (PNP)NiF 中提取 F(-) 导致（瞬态）（PNP）Ni（+）重排为类似的开环 [((t)Bu(2)PCH (2)SiMe(2)NSiMe(2)F)]Ni(CH(2)P(t)Bu(2))。在 CH(2)Cl(2) 或 C(6)H 中用 NaB(C(6)H(3)(CF(3))(2))(4) 从 (PNP)NiCl 中提取 Cl(-) (5)F 得到 (PNP)NiB(C(6)H(3)(CF(3))(2))(4)，这些反应中的关键中间体是 (PNP)Ni(+), [(PNP )Ni](+)，其中一个 Si-C 键（连同 N 和两个 P）捐赠给 Ni。这使得该 Si-C 键受到 F(-)、三氟甲磺酸酯和醇盐/醚（来自
• The Effect of One Valence Electron: Contrasting (PNP)Ni(CO) with (PNP)Ni(NO) to Understand the Half-Bent NiNO Unit
  作者：Benjamin C. Fullmer、Maren Pink、Hongjun Fan、Xiaofan Yang、Mu-Hyun Baik、Kenneth G. Caulton

  DOI：10.1021/ic702503m

  日期：2008.5.1

  "half-bent" NiNO unit and the intermediate coordination geometry result from a Ni --> NO charge transfer, which has a nonintegral value, resulting in a continuum between NO (+) (hence Ni (0)) and NO (-) (hence Ni (II)). This is related to the nonaxially symmetric character of the Ni --> NO back-donation caused by the (PNP) environment on Ni. Steric effects of ( t )Bu and even chelate constraints are

  （PNP）Ni自由基与NO的反应在混合时完成，以形成NO拉伸频率为1654 cm（-1）的1：1加合物。该反磁性产物的NMR数据表明C 2 v对称性与X射线结构相矛盾，X射线结构表明它在Ni处是非平面的，其几何形状介于平面和四面体之间。因此，平面几何形状是通量的过渡态，给出了时间平均的C 2 v对称性。X射线结构以及DFT计算表明，“半弯曲” NiNO单元和中间配位几何结构是由Ni-> NO电荷转移产生的，该电荷具有非整数值，从而导致NO（ +）（因此为Ni（0））和NO（-）（因此为Ni（II））。这与Ni的非轴对称特性有关-> Ni上的（PNP）环境不会引起反向捐赠。排除了（t）Bu的立体效应，甚至螯合约束，是造成异常电子和结构特征的原因。
• Influence of the d-Electron Count on CO Binding by Three-Coordinate [(^tBu₂PCH₂SiMe₂)₂N]Fe, -Co, and -Ni
  作者：Michael J. Ingleson、Benjamin C. Fullmer、Drew T. Buschhorn、Hongjun Fan、Maren Pink、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/ic7023764

  日期：2008.1.1

  Reduction of (PNP)MCI [PNP = ((Bu2PCH2SiMe2)-Bu-t)(2)N] with Mg gives three-coordinate, T-shaped (PNP)M for M = Fe(S = 3/2) and Ni. Their reactivity was tested toward CO; Ni binds one CO, but only reversibly (i.e., CO is completely lost in vacuum), and has a CO stretching frequency showing effective back-donation by Nil. The structure of (PNP)Ni(CO) is intermediate between planar and tetrahedral, in contrast to the planar d(8) analogue, (PNP)Co(CO), This structural reorganization on carbonylation changes the singly occupied molecular orbital from having negligible phosphorus character [no P hyperfine structure in the electron paramagnetic resonance (EPR) spectrum of (PNP)Ni] to having enough P character to have a triplet structure in the EPR spectrum of the CO. The presence of one fewer electron in (PNP)Fe (vs the Co analogue) leads to binding of two CO, and (PNP)Fe(CO)2 is characterized as a spin doublet with square-pyramidal structure. Density functional theory calculations strengthen the understanding of the structural and spectroscopic changes along this d(n) series (n = 7-9).
• [Ni{N(SiMe₂CH₂P<i>t</i>Bu₂)₂}]⁺: Direct Observation of Transannular SiC(sp³) Bond Coordination
  作者：Hongjun Fan、Benjamin C. Fullmer、Maren Pink、Kenneth G. Caulton

  DOI：10.1002/anie.200802654

  日期：2008.11.10