((t-Bu2PCH2SiMe2)2N)Ni | 1006375-77-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ((t-Bu2PCH2SiMe2)2N)Ni
• 英文别名: ((tBu2PCH2SiMe2)2N)Ni
• CAS: 1006375-77-4
• 化学式: C₂₂H₅₂NNiP₂Si₂
• 分子量: 507.47
• InChiKey: UHAJKJSHONBSIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.0
• 重原子数：
  28.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  14.1
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  ((t-Bu2PCH2SiMe2)2N)Ni 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  三坐标 NiII：追踪 [(tBu2PCH2SiMe2)2N]Ni+ 中不寻常的、简单的 Si−C(sp3) 键断裂的起源

  摘要：

  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

  DOI：

  10.1021/ja108426f
• 作为产物：
  描述：

  ((tBu2PCH2SiMe2)2N)Ni(CO) 以 not given 为溶剂， 生成 ((t-Bu2PCH2SiMe2)2N)Ni
  参考文献：
  名称：

  Influence of the d-Electron Count on CO Binding by Three-Coordinate [(^tBu₂PCH₂SiMe₂)₂N]Fe, -Co, and -Ni

  摘要：

  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).

  DOI：

  10.1021/ic7023764

文献信息

• Influence of the Metal Orbital Occupancy and Principal Quantum Number on Organoazide (RN₃) Conversion to Transition-Metal Imide Complexes
  作者：Amy N. Walstrom、Benjamin C. Fullmer、Hongjun Fan、Maren Pink、Drew T. Buschhorn、Kenneth G. Caulton

  DOI：10.1021/ic801035z

  日期：2008.10.6

  where PNP = ( (t)Bu 2PCH 2SiMe 2) 2N (-), promptly evolves N 2 and forms a P=N bond in the product (PNP=NPh)Ni (I). A similar reaction with (PNP)FeCl proceeds to form a P=N bond but without N 2 evolution, to furnish (PNP=N-N=NPh)FeCl. An analogous reaction with (PNP)RuCl occurs with a more dramatic redox change at the metal (and N 2 evolution), to give the salt composed of (PNP)Ru(NPh) (+) and (PNP)RuCl

  叠氮化苯与（PNP）Ni的反应（其中PNP =（（t）Bu 2PCH 2SiMe 2）2N（-））迅速生成N 2并在产物（PNP = NPh）Ni（I ）。与（PNP）FeCl的类似反应继续形成P = N键，但没有N 2放出，从而提供（PNP = NN = NPh）FeCl。与（PNP）RuCl的类似反应会发生，金属处的氧化还原变化更为明显（并且会释放N 2），从而生成由（PNP）Ru（NPh）（+）和（PNP）RuCl 3（-）组成的盐，以及等摩尔（PNP）Ru（NPh）。这些结果之间的对比可用来推断哪些条件有利于N 2损失以及将PhN 3中的NPh片段氧化结合到金属络合物中。
• 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。
• Evaluating the reducing power of 3-coordinate T-shaped NiI
  作者：Benjamin C. Fullmer、Hongjun Fan、Maren Pink、Kenneth G. Caulton

  DOI：10.1016/j.ica.2010.12.059

  日期：2011.4

  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.
• O/C Bond Cleavage of CO₂ by Ni^I
  作者：Benjamin C. Fullmer、Hongjun Fan、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ic701843u

  日期：2008.3.1

  Reaction of (PNP)Ni, where PNP is [((Bu2PCH2SiMe2)-Bu-t)(2)N](-1), with CO2 occurs rapidly even at -60 degrees C to form exclusively the product of transposition of the amide N and one CO2 oxygen: [((Bu2PCH2)-Bu-t SiMe2)(2)O]Ni(NCO). DFT(B3LYP) evaluation of several candidate intermediates for breaking two Si/N and one C/O bond and forming two Si/O and one N/C bond reveal species at and below the energy of the separated particles, and establish, the location of the spin densities in each.