(PtBu2CH2SiMe2)N(SiMe2CH2PtBu2)MgCl | 960079-55-4

• 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: (PtBu2CH2SiMe2)N(SiMe2CH2PtBu2)MgCl
• 英文别名: ((tBu2PCH2SiMe2)2N)MgCl；(t-Bu2PCH2SiMe2)2NMgCl
• CAS: 960079-55-4
• 化学式: C₂₂H₅₂NP₂Si₂*Cl*Mg
• 分子量: 508.538
• InChiKey: QXUBPMOTYNMERX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  29.0
• 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：

  (PtBu2CH2SiMe2)N(SiMe2CH2PtBu2)MgCl 、 chlorobis(cyclooctene)-iridium(I) dimer 以 四氢呋喃 为溶剂， 生成 (PtBu2CH2SiMe2)N(SiMe2CH2PtBuCMe2CH2)Ir(III)H
  参考文献：
  名称：

  Ir（III）上具有惊人的异构体偏好性，有利于轻松进行HC（sp（3））键裂解。

  摘要：

  物种（PNP）Ir（X）（Y），其中PNP = N（SiMe（2）CH（2）P（t）Bu（2））（2）（-1），带有X和Y卤化物， t）Bu基CH键通过跨Ir-N键的加成而杂合地分裂。

  DOI：

  10.1039/b908954c

文献信息

• Redox and Lewis Acid Reactivity of Unsaturated Os ^II
  作者：Nikolay Tsvetkov、Maren Pink、Hongjun Fan、Joo‐Ho Lee、Kenneth G. Caulton

  DOI：10.1002/ejic.201000503

  日期：2010.10

  2 ) 2 N} permits evaluation of its reactivity, both Lewis acidity and reducing power (i.e., ability to be oxidized). It binds two molecules of PhCN, into trans sites, but only one of ethylene, and, upon binding of one N 2 , there is heterolytic splitting of one tBu C-H bond to put the proton on amide N and the carbon on Os, leaving divalent metal in [PN(H)P*}Os(N 2 )(I)]. Two moles of H 2 add, forming

  [(PNP)OsI] PNP = (tBu 2 PCH 2 SiMe 2 ) 2 N} 的合成允许评估其反应性，路易斯酸度和还原能力（即，被氧化的能力）。它将两分子 PhCN 结合到反式位点，但只有一个乙烯，并且在结合一个 N 2 后，一个 tBu CH 键发生异裂分裂，将质子放在酰胺 N 上，将碳放在 Os 上，留下二价[PN(H)P*}Os(N 2 )(I)] 中的金属。两摩尔 H 2 添加，通过 HH 键杂裂形成 [PN(H)P}OsH(H 2 )I]。[(PNP)OsI] 的热解产生在 Os/N 键上添加 tBu 甲基 CH 键的产物，以及该中间体的净脱氢，形成卡宾配合物；释放的 H 2 形成 [(PNP)OsH 2 I]，并描述了 [(PNP)Os] 卤化氢的化学性质。与 O 2 发生反应时没有可检测的中间体，完全分裂 O=O 键，形成反式-[(PNP)Os(O) 2 I]
• [(^tBu₂PCH₂SiMe₂)₂N]Rh^I? Rapidly Reversible H−C(sp³) and H−C(sp²) Bond Cleavage by Rhodium(I)
  作者：Alexander Y. Verat、Maren Pink、Hongjun Fan、John Tomaszewski、Kenneth G. Caulton

  DOI：10.1021/om701165n

  日期：2008.1.1

  The product of the reaction of ((Bu2PCH2SiMe2)-Bu-t)(2)N- (MgCl+ salt) with [RhCl(cyclooctene)(2)](2) is a Rh-III complex where one Bu-t methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 x 4 C-H bonds of the four Bu-t groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at similar to 10(3) S-I at 25 degrees C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms eta(2)-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H)(2).
• 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).