(((t)Bu2PCH2SiMe2)2N)ReH4 | 714263-99-7

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: (((t)Bu2PCH2SiMe2)2N)ReH4
• CAS: 714263-99-7
• 化学式: C₂₂H₅₆NP₂ReSi₂
• 分子量: 639.019
• InChiKey: MBLJVIOLFMEXGL-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)ReH4 、 苯乙炔 以 正戊烷 为溶剂， 以70%的产率得到(((t)Bu2PCH2SiMe2)2N)Re(CCPh)2
  参考文献：
  名称：

  Terminal Acetylenes React to Increase Unsaturation in [(^tBu₂PCH₂SiMe₂)₂N]Re(H)₄

  摘要：

  (PNPtBu)Re(H)(4), where PNPtBu is ((Bu2PCH2SiMe2)-Bu-t)(2)N, reacts at 23 degreesC with RCdropCH (R = Bu-t, SiMe3, Ph) to give first H-2 and mirror-symmetric (PNPtBu)ReH3(CCR), then H-2 and C-2v symmetric (PNPtBu)Re(CCR)(2). The diacetylide compounds show temperature-independent paramagnetism and C-13 and P-31 chemical shifts far beyond their normal values for other (PNPtBu)ReXn, compounds. Single-crystal X-ray diffraction shows very similar structures for the cases R = Ph and R = SiMe3, each having an approximately C-2v geometry with equivalent acetylides with angleC-Re-C approximately 108degrees. No hydride or H-2 ligands are detected in final difference Fourier maps. DFT(B3PW91) calculations give minimum energy geometries of these species, of their products upon adding H-2, and of mechanistically significant analogues [(H2PCH2SiH2)(2)N] ReHnR'(m),H2-m, with n = 0, 2, m = 1, 2, and R' = H or Ph. These calculated geometries, when compared to those from X-ray diffraction, indicate that the isolated compounds have no hydride or H-2 ligands and are thus (PNP)Re-III(CCR)(2), making them more unsaturated than the reagent (PNP)Re-v(H)(4) by two electrons. Triplet state geometries of (PNP)ReXY are calculated and analyzed, as are their frontier orbitals.

  DOI：

  10.1021/om049424i
• 作为产物：
  描述：

  mer,cis-(((t-Bu)2PCH2SiMe2)2N)ReOCl2 、 氢气 在 Mg 、 Me₃SiCl 、 MgBr₂(Et₂O) 作用下， 以 乙醚 为溶剂， 以74%的产率得到(((t)Bu2PCH2SiMe2)2N)ReH4
  参考文献：
  名称：

  Transformation of Acyclic Alkenes to Hydrido Carbynes by (PNP^R)Re Complexes

  摘要：

  Synthesis of (PNPR)ReOCl2 (PNPR = (R2PCH2SiMe2)(2)N, R = Pr-i, Cy, and Bu-t) from (Me2S)(2)-ReOCl3 and (PNPR)MgCl is described. Magnesium and H-2 convert (PNPR)ReOCl2 first to (PNPR)ReO(H)(2) and then to (PNPR)Re(H)(4), the last being an operationally unsaturated species which can bind PMe3 or p-toluidine. Acyclic alkenes react with (PNPR)Re(H)(4) at 22 degreesC to give first (PNPR)Re(H)(2)(olefin) and then (PNPR)ReH(carbyne), in equilibrium with its eta(2)-olefin adduct. Re can also migrate to the terminal carbon of internal olefins to form a carbyne complex. Allylic C-SiMe3 or C-NH2 bonds are not broken, but OEt, OPh, and F vinyl substituents (X) are ultimately cleaved from carbon to give the Reequivalent toC-CH3 complex and liberate HX. DFT calculations, together with detection of intermediates for certain olefins, help to define a mechanism for these conversions.

  DOI：

  10.1021/ja031617u