((t)Bu2PCH2SiMe2)2N)CoI | 885669-55-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: ((t)Bu2PCH2SiMe2)2N)CoI
• 英文别名: bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;cobalt(2+);iodide
• CAS: 885669-55-6
• 化学式: C₂₂H₅₂CoINP₂Si₂
• 分子量: 634.678
• InChiKey: MYBNIYRCLDSAHL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.01
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  [((t)Bu2PCH2SiMe2)2N]CoC(H)SiMe3 以 氘代苯 为溶剂， 生成 ((t)Bu2PCH2SiMe2)2N)CoI
  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+

文献信息

• 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).