[tris(diisopropylphosphino)borate]CoI | 579444-64-7

• 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]CoI
• 英文别名: [PhB(PiPr)3]CoI；iodocobalt(1+);tris[di(propan-2-yl)phosphanylmethyl]-phenylboranuide
• CAS: 579444-64-7
• 化学式: C₂₇H₅₃BCoIP₃
• 分子量: 667.348
• InChiKey: IPGSMXDKSMENDL-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]CoI 在 汞 作用下， 以 四氢呋喃 为溶剂， 反应 0.39h， 生成
  参考文献：
  名称：

  Activations of all Bonds to Silicon (Si–H, Si–C) in a Silane with Extrusion of [CoSiCo] Silicide Cores

  摘要：

  The [BP3iPr]Co(I) synthon Na-(THF)(6){[BP3iPr]CoI} (1, [BP3iPr] = kappa(3)-PhB((CH2PPr2)-Pr-i)(3)(-)) reacts with PhSiH3 or SiH4 to form unusual {[BP2iPr](SiH2R)CoH2}=Si={H2Co[BP3iPr]} species (R = Ph, 2a; R = H, 2b; [BP2iPr] = kappa(2)-PhB((CH2PPr2)-Pr-i)(2)) that result from activation of all Si-H and Si-C bonds in the starting silanes. Solution-spectroscopic data (multinuclear NMR, IR) for 2a,b, and the solid-state structure of 2a, indicate substantial Co=Si=Co multiple bonding and minimal interaction of the core Si atom with nearby hydride ligands. In the presence of 4-dimethylaminopyridine (DMAP), 1 reacts with PhSiH3 to give [BP3iPr](H)(2)CoSiHPh(DMAP) (3). Complexes 2a,b eliminate RSiH3 upon thermolysis in the presence of DMAP to generate {[BP2iPr]Co(NC5H3NMe2)}=Si={H2Co[BP3iPr]} (4).

  DOI：

  10.1021/jacs.9b04265
• 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]CoI
  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

文献信息

• Spin-State Tuning at Pseudotetrahedral d⁷ Ions:  Examining the Structural and Magnetic Phenomena of Four-Coordinate [BP₃]Co^II−X Systems
  作者：David M. Jenkins、Jonas C. Peters

  DOI：10.1021/ja045310m

  日期：2005.5.1

  new cobalt(II) complexes [PhBP(3)]CoOSiPh(3) (2), [PhBP(3)]CoO(4-(t)()Bu-Ph) (3), [PhBP(3)]CoO(C(6)F(5)) (4), [PhBP(3)]CoSPh (5), [PhBP(3)]CoS(2,6-Me(2)-Ph) (6), [PhBP(3)]CoS(2,4,6-(i)()Pr(3)-Ph) (7), [PhBP(3)]CoS(2,4,6-(t)()Bu(3)-Ph) (8), [PhBP(3)]CoSSiPh(3) (9), [PhBP(3)]CoOSi(4-NMe(2)-Ph)(3) (10), [PhBP(3)]CoOSi(4-CF(3)-Ph)(3) (11), [PhBP(3)]CoOCPh(3) (12), [PhBP(i)()(Pr)(3)]CoOSiPh(3) (14), and

  由三（膦基）硼酸盐 [BP(3)] 配体 [PhBP(3)] 和[PhBP(i)()(Pr)(3)] ([PhB(CH(2)PPh(2))(3)](-) 和 [PhB(CH(2)P(i)()Pr( 2))(3)](-)，分别进行了描述。除了低温 EPR 和可变温度 SQUID 磁化数据外，还提供了新的钴 (II) 配合物 [PhBP(3)]CoOSiPh(3) 的标准 (1)H NMR、光学、电化学和溶液磁数据(2), [PhBP(3)]CoO(4-(t)()Bu-Ph) (3), [PhBP(3)]CoO(C(6)F(5)) (4), [PhBP (3)]COSa href=https://www.molaid.com/MS_15603 target="_blank">SPh (5), [PhBP(3)]COS(2,6-Me(2)-Ph) (6), [PhBP(3)]COS(2,4,6-(i)( )Pr(3)-Ph) (7), [PhBP(3)]COS(2,4,6-(t)()Bu(3)-Ph) (8)
• Dinitrogen Chemistry from Trigonally Coordinated Iron and Cobalt Platforms
  作者：Theodore A. Betley、Jonas C. Peters

  DOI：10.1021/ja036687f

  日期：2003.9.1

  This report establishes that trigonally coordinated "[PhBPiPr3]M" platforms (M = Fe, Co) will support both pi-acidic (N2) and pi-basic (NR) ligands at a fourth binding site. The N2 complexes of iron that are described are the first thoroughly characterized examples to exhibit a 4-coordinate geometry. Methylation of monomeric Fe0(N2)-} and Co0(N2)-} species successfully derivatizes the beta-N atom

  该报告确定了三角协调的“[PhBPiPr3]M”平台（M = Fe，Co）将在第四个结合位点同时支持 pi 酸性（N2）和 pi 碱性（NR）配体。所描述的铁的 N2 络合物是第一个完全表征的例子，展示了 4 坐标几何。单体 Fe0(N2)-} 和 Co0(N2)-} 物质的甲基化成功衍生出配位 N2 配体的 β-N 原子并提供二氮杂产物 FeII(N2Me)} 和 CoII(N2Me)}，分别。单核 M0(N2)- 物种的单电子氧化产生双核和合成通用 MI(N2)MI 复合物。这些后一种物质为“[PhBPiPr3]MI”亚基的化学提供了干净的途径。例如，