(((t-Bu)2PCH2SiMe2)2N)MgCl*(1,4-dioxane) | 568593-26-0

• 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-Bu)2PCH2SiMe2)2N)MgCl*(1,4-dioxane)
• 英文别名: [((t)Bu2PCH2SiMe2)2N]MgCl*(dioxane)；Mg(N(SiMe2CH2P-t-Bu2)2)Cl(dioxane)
• CAS: 568593-26-0
• 化学式: C₄H₈O₂*C₂₂H₅₂ClMgNP₂Si₂
• 分子量: 596.644
• InChiKey: GYVIASCMMUKRCM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.66
• 重原子数：
  35.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.56
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  cobalt(II) iodide 、 (((t-Bu)2PCH2SiMe2)2N)MgCl*(1,4-dioxane) 以 四氢呋喃 为溶剂， 以54%的产率得到((t)Bu2PCH2SiMe2)2N)CoI
  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

• An evaluation of monovalent osmium supported by the PNP ligand environment
  作者：Nikolay Tsvetkov、Hongjun Fan、Kenneth G. Caulton

  DOI：10.1039/c0dt00989j

  日期：——

  Nitrogen is essential to reaction of (PNP)OsI (PNP is N(SiMe2CH2PtBu2)2) and Mg powder in THF, to give equimolar (PNP)OsH(N2) and hydrido carbene [(tBu2PCH2SiMe2)N(SiMe2CH2PtBu(CMe2CH)]OsH. This reaction is attributed to H2 evolution from solid magnesium, rather than high energy H atom transfer between molecules, but relies also on the strong π-basicity of Os in favoring α-H migration from the metallated tBu group on Os to form the second product, the hydrido carbene species. The path to two different products begins because the simple N2 adduct of (PNP)OsI undergoes spontaneous heterolytic H–C splitting of the tBu methyl group, to produce a secondary amine intermediate [(tBu2PCH2SiMe2)N(H)(SiMe2CH2PtBu(CMe2CH2)]OsI(N2) which can then be dehydrohalogenated by Mg. The analogous reaction for (PNP)RuCl shows production of only (PNP)RuH(N2), with none of the hydride carbene dehydrogenation product. Comparative (Ruvs. Os) DFT calculations reveal the reaction steps where the Os analog is much more exothermic, accounting for certain reaction selectivities.

  氮是 (PNP)OsI （PNP 为 N(SiMe2CH2PtBu2)2）和镁粉在四氢呋喃中发生反应的必要条件，反应生成等摩尔 (PNP)OsH(N2) 和碳氢化物 [(tBu2PCH2SiMe2)N(SiMe2CH2PtBu(CMe2CH)]OsH。这一反应归因于从固体镁中演化出的 H2，而不是分子间的高能 H 原子转移，但也依赖于 Os 的强π碱性，有利于 α-H 从 Os 上的金属化 tBu 基团迁移，形成第二种产物，即碳化氢。通向两种不同产物的路径开始于 (PNP)OsI 的简单 N2 加合物自发地发生 tBu 甲基的异解 H-C 分裂，生成仲胺中间体[(tBu2PCH2SiMe2)N(H)(SiMe2CH2PtBu(CMe2CH2)]OsI(N2)，然后可由 Mg 进行脱氢卤化。(PNP)RuCl 的类似反应只生成 (PNP)RuH(N2)，没有碳氢化合物脱氢产物。比较（Ruvs. Os）DFT 计算揭示了 Os 类似物放热更多的反应步骤，从而解释了某些反应的选择性。
• Amido/phosphine pincer hydrides of ruthenium
  作者：Lori A. Watson、Joseph N. Coalter III、Oleg Ozerov、Maren Pink、John C. Huffman、Kenneth G. Caulton

  DOI：10.1039/b206202j

  日期：2003.1.20

  The chemistry of the ligand (R2PCH2SiMe2)2N− (R=cyclohexyl and tBu), “PNP-R”, on ruthenium is developed, including RuH(PNP-Cy)(PPh3) and (HPNP-R)RuH3Cl. The latter contains a protonated nitrogen (i.e., amine as a donor to Ru) and one H2 ligand (X-ray structure for R=tBu). This compound can be dehydrohalogenated to give (PNP-Cy)RuH3, which undergoes H/D exchange of D2 into its cyclohexyl rings, and

  配位体的化学性质（R 2 PCH 2森达2）2 ñ - （R =环己基和吨丁基），“PNP-R”，钌被显影，包括期RuH（PNP-CY）（PPH 3）和（HPNP -R）RuH 3 Cl。后者包含质子化的氮（即，胺作为Ru的供体）和一个H 2配体（R = t Bu的X射线结构）。该化合物可以脱卤化氢得到（PNP-Cy）RuH 3，其经过D 2的H / D交换进入其环己基环，并且本身被过量的H 2 C脱氢CHR得到[Cy 2 PCH 2 SiMe 2 NSiMe 2 CH 2 PCy（C 6 H 8）] Ru，该Ru包含与Ru结合的三脱氢环己基环π-烯丙基。（PNP-Cy）RuH 3与二氢呋喃反应，得到杂原子稳定的卡宾配合物（PNP-Cy）RuH [ CO（CH 2）3 ]。
• Nitrogen-Ligated Iron Complexes: Photolytic Approach to the FeN⁺ Moiety
  作者：Drew Buschhorn、Maren Pink、Hongjun Fan、Kenneth G. Caulton

  DOI：10.1021/ic702279b

  日期：2008.6.1

  is thermally stable, it is photosensitive to lose N2 and form [(PNPN)Fe]2,in which the nitride ligand has formed a double bond to one phosphorus, and this N bridges to a second iron to form a 2-fold symmetric dimer. The reaction energy to form the (undetected) monomeric [eta3- tBu2PCH2SiMe2NSiMe2CH2PtBu2N]Fe is -15.9 kcal/mol, so this PIII --> PV oxidation is favorable. The eta2 version of this same

  报道了（PNP）FeCl，（PNP）Fe [NH（二甲苯基）]和（PNP）FeN3的合成（PNP ＝（tBu2PCH2SiMe2）2N-）。虽然叠氮化物是热稳定的，但它是光敏性的，会损失N2并形成[（PNPN）Fe] 2，其中氮化物配体已与一个磷形成双键，并且该N桥连至第二个铁以形成2-折叠对称二聚体。形成（未检测到）单体[η3-tBu2PCH2SiMe2NSiMe2CH2PtBu2N] Fe的反应能量为-15.9 kcal / mol，因此该PIII-> PV氧化是有利的。这个相同物种的eta2版本在23.7 kcal / mol下不稳定，这表明一个P-> Fe键的丢失是由二聚作用引起的，因此它不会先于并引起二聚作用。与Ru类似物进行比较。
• Transformation of Acyclic Alkenes to Hydrido Carbynes by (PNP^R)Re Complexes
  作者：Oleg V. Ozerov、Lori A. Watson、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ja031617u

  日期：2004.5.1

  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.
• Four-Coordinate, Planar Ru(II). A Triplet State as a Response to a 14-Valence Electron Configuration
  作者：Lori A. Watson、Oleg V. Ozerov、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ja035166p

  日期：2003.7.1

  The ligand (tBu2PCH2SiMe2)2N1- (PNP) in [PNP]RuCl leads to an intermediate spin ground state, S = 1, which has been characterized by NMR and X-ray diffraction as having a planar structure. This spin state is attributed in part to N --> Ru pi donation. DFT calculations confirm that the singlet state lies higher in energy and is nonplanar. The molecule is converted to a diamagnetic product by addition of 2 mol of PhCN. The half-filled orbitals of the S = 1 state are suggested to be the reason agostic interactions do not compensate for the 14-valence electron count.