[((t)Bu2PCH2SiMe2)2N]Co(I) | 879549-47-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [((t)Bu2PCH2SiMe2)2N]Co(I)
• 英文别名: ((t)Bu2PCH2SiMe2)2N)Co
• CAS: 879549-47-0
• 化学式: C₂₂H₅₂CoNP₂Si₂
• 分子量: 507.773
• InChiKey: IHWKYQYIXZBKOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [((t)Bu2PCH2SiMe2)2N]Co(I) 、 加尔万氧基自由基 以 氘代苯 为溶剂， 生成 [((t)Bu2PCH2SiMe2)2N]Co(galvinoxyl)
  参考文献：
  名称：

  Redox Chemistry of the Triplet Complex (PNP)Co^I

  摘要：

  Reaction of PNPCo, where PNP is ((Bu2PCH2SiMe2)-Bu-t)(2)N-, with the persistent radical galvinoxyl, G, gives PNPCo(parallel to)G, a nonplanar S = 3/2 species. Reaction with PhCH2Cl or with 0.5 mol I-2 gives PNPCoX (X = Cl or I, respectively), but additional I-2, Seeking Co-parallel to|, gives instead oxidation at phosphorus: ((Bu2P)-Bu-t(I)(CH2SiMe2NSiMe2CH2PBu2)-Bu-t)CoI2. Hydrogen-atom transfer reagents fail to give PNPCoH, but H-2 gives instead PNPCo(H)2, a result rationalized thermodynamically based on DFT calculations. Multiple equiv of PhSiH3 give a product of Co(V), where N/SiPh and P/Si bonds have formed. N2CH(SiMe3) gives a 1:1 adduct of PNPCo, whose metric parameters suggest partial oxidation above Col; N2CHPh gives a 1:1 adduct but with very different spectroscopic features. PhN3 reacts fast, via several intermediates detected below 0 degrees C, to finally release N-2 and form a Col product where one phosphorus has been oxidized, PN(P = NPh)Co. Whereas PNPCo(N-3) resists loss of N-2 on heating, one electron oxidation gives a rapid loss of N-2, and the remaining nitride nitrogen is quickly incorporated into the chelate ligand, giving [(Bu2PCH2SiMe2NSiMe2NP)-Bu-t(Bu-t(2))=CH2Co]. O-2 or Phl = O generally gives products where one or both phosphorus centers are converted to its oxide, bonded to cobalt.

  DOI：

  10.1021/ja074378+
• 作为产物：
  描述：

  ((t)Bu2PCH2SiMe2)2N)CoI 在 sodium naphthalide 作用下， 以 四氢呋喃 为溶剂， 生成 [((t)Bu2PCH2SiMe2)2N]Co(I)
  参考文献：
  名称：

  Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo

  摘要：

  The compounds (PNP)CoX, where PNP is ((Bu2PCH2SiMe2)-Bu-t)(2)N- and X is Cl, l, N-3, OAr, OSO2CF3 and N(H)Ar, are reported. Some of these show magnetic susceptibility, color, and H-1 NMR evidence of being in equilibrium between a blue, tetrahedral S = 3/2 state and a red, planar S = 1/2 state; the equilibrium populations are influenced by subtle solvent effects (e.g., benzene and cyclohexane are different), as well as by temperature. Attempted oxidation to Co(III) with O-2 occurs instead at phosphorus, giving [P(O)NP(O)]CoX species. The single O-atom transfer reagent Phl=O likewise oxidizes P. Even l(2) oxidizes P to give the pendant phosphonium species ((t)Bu2P(l)CH2SiMe2-(NSiMe2CH2PBU2)-B-t)Col(2) with a tetrahedral S = 3/2 cobalt; the solid-state structure shows intermolecular Pl center dot center dot center dot lCo interactions. Attempted alkyl metathesis of PNPCoX inevitably results in reduction, forming PNPCo, which is a spin triplet with planar T-shaped coordination geometry with no agostic interaction. Triplet PNPCo binds N-2(weakly) and CO (whose low CO stretching frequency indicates strong PNP -> Co donor power), but not ethene or MeCCMe.

  DOI：

  10.1021/ic701171p

文献信息

• Metal-Dependent Reactivity Differences for Transients Formed By Flash Photolysis of (PNP)M(CO), M = Co and Rh
  作者：R. Dale Rimmer、David C. Grills、Hongjun Fan、Peter C. Ford、Kenneth G. Caulton

  DOI：10.1021/ja076357l

  日期：2007.12.1

  Spin triplet (PNP)Co adds one CO according to a rate law first-order in each reagent with k = 9.3 × 105 M-1 s-1. In contrast, the transient produced by photodissociation of CO from (PNP)Rh(CO) forms, within 10 ns, the Rh(III) species [η4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH, and this adds CO with a second-order rate constant of 6 × 106 M-1 s-1. The resulting monocarbonyl then slowly (k = 3 × 101

  自旋三重态 (PNP)Co 根据 k = 9.3 × 105 M-1 s-1 的每个试剂中的一阶速率定律添加一个 CO。相比之下，CO 从 (PNP)Rh(CO) 光解产生的瞬态在 10 ns 内形成 Rh(III) 物种 [η4-tBu2PCH2SiMe2NSiMe2CH2PtBu(CMe2CH2)]RhH，这以二阶速率添加 CO常数为 6 × 106 M-1 s-1。生成的单羰基然后缓慢地 (k = 3 × 101 s-1) 还原性地消除 H 和 C(sp3) 以重新形成 (PNP)Rh(CO)。前两个速率常数支持三重态 (PNP)Co 和单重态 (PNP)Co(CO) 之间的自旋交叉导致速率抑制的想法。
• Reducing Power of Three-Coordinate Cobalt(I)
  作者：Michael J. Ingleson、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ja0607279

  日期：2006.4.5

  Carbon monoxide adds easily to (PNP)Co, PNP = N(SiMe2CH2PtBu2)2, to give (PNP)Co(CO), whose nuco value of 1885 cm-1 suggests much back-donation, and thus an easily oxidized Co(I) in (PNP)Co. However, Co(III) is inaccessible from (PNP)Co by oxidation with I2, the products being first (PNP)CoI, then the zwitterion [ItBu2PCH2SiMe2NSiMe2CH2PtBu2]CoI2. The potential two-electron oxidant N2CH(SiMe3) reacts with (PNP)Co to form a 1:1 "adduct", whose crystal structure is most consistent with oxidation of Co(I), but not fully to Co(III).
• Three-Coordinate Co(I) Provides Access to Unsaturated Dihydrido-Co(III) and Seven-Coordinate Co(V)
  作者：Michael Ingleson、Hongjun Fan、Maren Pink、John Tomaszewski、Kenneth G. Caulton

  DOI：10.1021/ja0572452

  日期：2006.2.1

  The three-coordinate, T-shaped Co(I) complex, PNPCo (PNP = [(tBu2PCH2SiMe2)2N-], is readily synthesized by magnesium reduction of divalent PNPCoCl. Triplet (S = 1) PNPCo is coordinatively and electronically unsaturated and undergoes a thermally reversible oxidative addition reaction with H2, producing trivalent PNPCo(H)2. In contrast, the reaction with excess primary silane PhSiH3 quantitatively generates the base-stabilized silylene Co(V) compound kappa2-tBu2PCH2Me2SiNSiMe2CH2tBu2P(H)Si=}Co(H)3(SiH2Ph)2.