[tris(diisopropylphosphino)borate]CoCl | 579444-63-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [tris(diisopropylphosphino)borate]CoCl
• 英文别名: chlorocobalt(1+);tris[di(propan-2-yl)phosphanylmethyl]-phenylboranuide
• CAS: 579444-63-6
• 化学式: C₂₇H₅₃BClCoP₃
• 分子量: 575.896
• InChiKey: TWJQWKQJYYUBDS-UHFFFAOYSA-M

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：

  [tris(diisopropylphosphino)borate]CoCl 、 (2,4,6-Me3C6H2)2SiHLi(THF)2 以 正戊烷 为溶剂， 反应 0.05h， 以28%的产率得到
  参考文献：
  名称：

  三膦硼酸根配体负载的晚3d过渡金属的亚甲硅烷基配合物

  摘要：

  探索了[BP 3 R ] MX（[BP 3 R ] = PhB（CH 2 PR 2）3 –，R = Ph，i Pr; M = Ni，Co，Fe; X =卤化物）的配合物作为生成平台第一排金属甲硅烷基络合物的制备。[BP 3 Ph ] NiCl或[BP 3 i Pr ] CoCl与（THF）2 LiSiHMes 2的直接甲硅烷基化导致形成亚甲硅烷基络合物[BP 3 Ph ] Ni（μ-H）（SiMes 2）和[BP 3 i Pr ] Co（μ-H）（SiMes 2）， 分别。相反，[BP 3 i Pr ] FeBr与（THF）2 LiSiHMes 2反应生成烷基铁[BP 3 i Pr ] Fe（CH 2 -2-（SiH 2 Mes）-3,5-Me 2 C 6 H 2），是预期的甲硅烷基或甲硅烷基络合物的结构异构体。镍的制备苄基配合物[BP 3博士]镍（η 2 -Bn）允许加成-消除化学勘探从

  DOI：

  10.1021/acs.organomet.8b00635
• 作为产物：
  描述：

  lithium,methanidyl-di(propan-2-yl)phosphane 在 TMEDA 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 [tris(diisopropylphosphino)borate]CoCl
  参考文献：
  名称：

  The Strong-Field Tripodal Phosphine Donor, [PhB(CH₂PⁱPr₂)₃]^-, Provides Access to Electronically and Coordinatively Unsaturated Transition Metal Complexes

  摘要：

  This paper introduces a sterically encumbered, strong-field tris(diisopropylphosphino)borate ligand, [PhBp(3)(iPr)] ([PhBP3iPr] = [PhB((CH2PPr2)-Pr-i)(3)](-)), to probe aspects of its conformational and electronic characteristics within a host of complexes. To this end, the TI(I) complex, [PhBP3iPr]TI (1), was synthesized and characterized in the solid-state by X-ray diffraction analysis. This precursor proves to be an effective transmetallating agent, as evidenced by its reaction with the divalent halides FeCl2 and CoX2 (X = Cl, 1) to produce the monomeric, 4-coordinate, high-spin derivatives [PhBP3iPr]FeCl (2) and [PhBP3iPr]CoX (X = Cl (3), 1 (4)) in good yield. Complexes 2-4 were each characterized by X-ray diffraction analysis and shown to be monomeric in the solid-state. For conformational and electronic comparison within a system exhibiting higher than 4-coordination, the 16-electron ruthenium complexes {[PhBP3iPr]Ru(mu-Cl)}(2) (5) and {[PhBP3]Ru(mu-Cl)}(2) (6) were prepared and characterized ([PhBP3] = [PhB(CH2PPh2)(3)](-)). The chloride complexes 2 and 3 reacted with excess CO to afford the divalent, monocarbonyl adducts [PhBP3iPr]- FeCl(CO) (7) and [PhBP3iPr]CoCl(CO) (8), respectively. Reaction of 4 with excess CO resulted in the monovalent, dicarbonyl product [PhBP3iPr]Co-I(CO)(2) (9). Complexes 5 and 6 also bound CO readily, providing the octahedral, 18-electron complexes [PhBP3iPr]RuCl(CO)(2) (10) and [PhBP3]RuCl(CO)(2) (11), respectively. Dimers 5 and 6 were broken up by reaction with trimethylphosphine to produce the mono-PMe3 adducts [PhBP3iPr]RuCl(PMe3) (12) and [PhBP3]RuCl(PMe3) (13). Stoichiometric oxidation of 3 with dioxygen provided the 4-electron oxidation product [PhB(CH2P(O)Pr-i(2))(2)((CH2PPr2)-Pr-i)]CoCl (14), while exposure of 3 to excess oxygen results in the 6-electron oxidation product [PhB(CH2P(O)Pr-i(2))(3)]CoCl (15). Complexes 2 and 4 were characterized via cyclic voltammetry to compare their redox behavior to their [PhBP3] analogues. Complex 4 was also studied by SQUID magnetization and EPR spectroscopy to confirm its high-spin assignment, providing an interesting contrast to its previously described low-spin relative, [PhBP3]CoI. The difference in spin states observed for these two systems reflects the conformational rigidity of the [PhBp(3)(iPr)] ligand by comparison to [PhBP3], leaving the former less able to accommodate a JT-distorted electronic ground state

  DOI：

  10.1021/ic0343096