[(PMe2Ph)4Pd2B10H10] | 1319714-65-2

• 英文名称: [(PMe2Ph)4Pd2B10H10]
• 英文别名: [(PMe₂Ph)₄Pd₂B₁₀H₁₀]
• CAS: 1319714-65-2
• 化学式: C₃₂H₅₄B₁₀P₄Pd₂
• 分子量: 883.626
• InChiKey: JWGPFTOBPZLWGA-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：

  [(PMe2Ph)4Pd2B10H10] 以 not given 为溶剂， 生成 [(Cl)(PMe2Ph)3Pd2B10H9(PMe2Ph)]
  参考文献：
  名称：

  Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

  摘要：

  Metallaborane compounds containing two adjacent metal atoms, [(PMe2Ph)(4)MM'B10H10] (where MM' = Pt-2., 1; PtPd, 7; Pd-2, 8), have been synthesized, and their propensity to sequester O-2, CO, and SO2 and to then release them under pulsed and continuous irradiation are described. Only [(PMe2Ph)(4)Pt2B10H10], 1, undergoes reversible binding of O-2 to form [(PMe2Ph)(4)(O-2)Pt2B10H10] 3, but solutions of 1, 7, and 8 all quantitatively take up CO across their metal-metal vectors to form [(PMe2Ph)(4)(CO)Pt2B10H10] 4, [(PMe2Ph)(4)(CO)PtPdB10H10] 10, and [(PMe2Ph)(4)(CO)Pd2B10H10] 11, respectively. Crystallographically determined interatomic M-M distances and infrared CO stretching frequencies show that the CO molecule is bound progressively more weakly in the sequence {PtPt} > {PtPd} > {PdPd}. Similarly, SO2 forms [(PMe2Ph)(4)(SO2)Pt2B10H10] 5, [(PMe2Ph)(4)(SO2)PtPdB10H10] 12, and [(PMe2Ph)(4)(SO2)Pd2B10H10] 13 with progressively weaker binding of the SO2 molecule. The uptake and release of gas molecules are accompanied by changes in their absorption spectra. Nanosecond transient absorption spectroscopy clearly shows that the O-2 and CO molecules are liberated from the bimetallic binding site with high quantum yields of about 0.6. For 3, in addition to dioxygen release in the triplet ground state, singlet oxygen O-2((1)Delta(g)) was also detected with a quantum yield < 0.01. In most cases, the release and rebinding of the gas molecules can be cycled with little photodegradation of the compounds. Femtosecond transient absorption spectroscopy further reveals that the photorelease of the O-2 and CO molecules, from 3 and 4 respectively, is an ultrafast process taking place on a time scale of tens of picoseconds. For SO2, the release is even faster (< 1 ps), but only in the case of mixed metal PtPd adducts, most probably because of the metal-metal bonding asymmetry in the mixed metal clusters; for the corresponding symmetric Pt-2 and Pd-2 adducts, 5 and 13, the release of SO2 is significantly slower (> 1 ns). All these compounds may have potential to serve as light-triggered local and instantaneous sources of the studied gases.

  DOI：

  10.1021/ic200374k
• 作为产物：
  描述：

  [(PMe2Ph)2PdB10H12] 、 dichlorobis(dimethylphenylphosphine)palladium(II) 在 KHB(C₂H₅)3 作用下， 以 甲苯 为溶剂， 以57%的产率得到[(PMe2Ph)4Pd2B10H10]
  参考文献：
  名称：

  Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

  摘要：

  Metallaborane compounds containing two adjacent metal atoms, [(PMe2Ph)(4)MM'B10H10] (where MM' = Pt-2., 1; PtPd, 7; Pd-2, 8), have been synthesized, and their propensity to sequester O-2, CO, and SO2 and to then release them under pulsed and continuous irradiation are described. Only [(PMe2Ph)(4)Pt2B10H10], 1, undergoes reversible binding of O-2 to form [(PMe2Ph)(4)(O-2)Pt2B10H10] 3, but solutions of 1, 7, and 8 all quantitatively take up CO across their metal-metal vectors to form [(PMe2Ph)(4)(CO)Pt2B10H10] 4, [(PMe2Ph)(4)(CO)PtPdB10H10] 10, and [(PMe2Ph)(4)(CO)Pd2B10H10] 11, respectively. Crystallographically determined interatomic M-M distances and infrared CO stretching frequencies show that the CO molecule is bound progressively more weakly in the sequence {PtPt} > {PtPd} > {PdPd}. Similarly, SO2 forms [(PMe2Ph)(4)(SO2)Pt2B10H10] 5, [(PMe2Ph)(4)(SO2)PtPdB10H10] 12, and [(PMe2Ph)(4)(SO2)Pd2B10H10] 13 with progressively weaker binding of the SO2 molecule. The uptake and release of gas molecules are accompanied by changes in their absorption spectra. Nanosecond transient absorption spectroscopy clearly shows that the O-2 and CO molecules are liberated from the bimetallic binding site with high quantum yields of about 0.6. For 3, in addition to dioxygen release in the triplet ground state, singlet oxygen O-2((1)Delta(g)) was also detected with a quantum yield < 0.01. In most cases, the release and rebinding of the gas molecules can be cycled with little photodegradation of the compounds. Femtosecond transient absorption spectroscopy further reveals that the photorelease of the O-2 and CO molecules, from 3 and 4 respectively, is an ultrafast process taking place on a time scale of tens of picoseconds. For SO2, the release is even faster (< 1 ps), but only in the case of mixed metal PtPd adducts, most probably because of the metal-metal bonding asymmetry in the mixed metal clusters; for the corresponding symmetric Pt-2 and Pd-2 adducts, 5 and 13, the release of SO2 is significantly slower (> 1 ns). All these compounds may have potential to serve as light-triggered local and instantaneous sources of the studied gases.

  DOI：

  10.1021/ic200374k

文献信息

• Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters
  作者：Jonathan Bould、Michael G.S. Londesborough、John D. Kennedy、Ramón Macías、Rudolph E.K. Winter、Ivana Císařová、Pavel Kubát、Kamil Lang

  DOI：10.1016/j.jorganchem.2013.02.010

  日期：2013.12

  The bimetalladodecaborane cluster compound [(PMe2Ph)(4)Pt2B10H10] 1, quantitatively reacts with EtNC at room temperature to afford [(EtNC)(PMe2Ph)(3)}(mu-EtNC) Pt2B10H10] 3 in which one molecule of EtNC replaces a terminal PMe2Ph ligand, and a second molecule of EtNC bridges the PtePt vector. The metalbridging EtNC molecule can be ejected from 3, either by irradiation with UV light, or via displacement with CO to form [(EtNC)(PMe2Ph)(3)}(mu-CO) Pt2B10H10] 4. The CO-bridge may then in turn be replaced with SO2 to give [(EtNC)(PMe2Ph)(3)}(mu-SO2) Pt2B10H10] 5. If 3 is allowed to react directly with SO2 then the SO2 molecule takes up a bridging position and the bridging EtNC displaces a terminal metal-bound phosphine to afford [(EtNC)(2)(PMe2Ph)(2)}(mu-SO2) Pt2B10H10] 6. The transient absorption spectrum of 3 under UV illumination is investigated and shows that the bridging isonitrile is ejected to produce a transient spectrum very similar to that of [(PMe2Ph)(4)Pt2B10H10] 1. Reaction of [(PMe2Ph)(4)Pd2B10H10] 7, viz. the dipalladium analogue of 1, with EtNC results in the displacement of two PMe2Ph phosphine ligands forming [(EtNC)(2)(PMe2Ph)(2)} Pd2B10H10] 8, which has no bridging EtNC unit and which shows only a weak ability to form an adduct with SO2. DFT calculations at the B3LYP/6-31G* level mirror the observed data well. (C) 2013 Elsevier B. V. All rights reserved.