dichlorobis(1,3,5-triaza-7-phosphaadamantane)nickel(II) | 214891-94-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环化合物
• 英文名称: dichlorobis(1,3,5-triaza-7-phosphaadamantane)nickel(II)
• 英文别名: dichloronickel;1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane
• CAS: 214891-94-8；226400-44-8
• 化学式: C₁₂H₂₄Cl₂N₆NiP₂
• 分子量: 443.906
• InChiKey: WLJAQYVVGHHKSF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  dichlorobis(1,3,5-triaza-7-phosphaadamantane)nickel(II) 以 甲醇 、 水 为溶剂， 生成 carbonyltris(1,3,5-triaza-7-phosphaadamantane)nickel(0)
  参考文献：
  名称：

  Water-Soluble Organometallic Compounds. 7.¹ Further Studies of 1,3,5-Triaza-7-Phosphaadamantane Derivatives of Group 10 Metals, Including Metal Carbonyls and Hydrides

  摘要：

  The syntheses of Ni(PTA)(4) (5), Pd(PTA)(4) (6), and Pt(PTA)(4) (8) are accomplished through the reduction of the (MCl2)-Cl-II salts in water with excess 1,3,5-triaza-7-phosphaadamantane (PTA). The products are obtained as partially protonated derivatives with protonation occurring at the nitrogen atoms of the bound PTA ligands. Crystal structures illustrating the monoprotonated and bis-protonated derivatives of 8, [Pt(PTA)(3)(PTAH)][Cl] (1S) and [Pt(PTA)(2)](PTA)(3)[BF4](2) (2S), are reported. The crystal structure of an intermediate along the reduction pathway, [PdCl(PTA)(3)][Cl] (7), is also presented, showing a trans influence whereby the Pd-P bond length trans to the Cl- ligand is shorter, 2.238(3) Angstrom, than the average Pd-P bond length cis to the Cl- ligand, 2.334(2) Angstrom. Complex 8 is also protonated at the metal center to form [(H)Pt(PTA)(4)][X], where X = Cl-, BF4-, HCO3-, and C3H5CO2-, through the addition of weak acids such as CO2/H2O, NH4Cl, PTAH(+)Cl(-), HPy+BF4-, and crotonic acid. Addition of strong acids such as HCl or HBF4 results in protonation at the PTA ligands. Thereby, the Pt metal center is shown to have a pK(a) between 7.44 and 9.25. The bound PTA ligands on complex 8 have a pK(a) below 4.69 but above 2.12. Ni(CO)(4-n)(PTA)(n) derivatives are also reported for n = 3 (9), 2 (10), and 1 (11). Using LR data of 11, PTA is determined to have an electronic parameter (chi) as defined by Tolman to be 15.3 cm(-1), indicating PTA to be slightly less donating than PPh3, where chi = 12.8 cm(-1). Complex 10 is crystallized out of a MeOH/ether solution maintained at -15 degrees C and characterized by X-ray crystallography. It is a distorted tetrahedron and has a crystallographically determined Tolman cone angle of PTA of 103 degrees. Monitored reactions of Ni(PTA)(4) with CO in water via in situ IR techniques show that the rate observed for the dissociation of PTA to provide Ni(CO)(PTA)(3) is 7.92 x 10(-4) s(-1) at 20 degrees C. This rate, along with P-31 NMR results, indicates that the M-0(TA)(4) complexes exhibit little dissociation and slow exchange of the bound PTA ligands.

  DOI：

  10.1021/ic981243j
• 作为产物：
  描述：

  1,3,5-三氮杂-7-磷杂金刚烷 、 nickel dichloride 以 甲醇 为溶剂， 以85%的产率得到dichlorobis(1,3,5-triaza-7-phosphaadamantane)nickel(II)
  参考文献：
  名称：

  Water-Soluble Organometallic Compounds. 7.¹ Further Studies of 1,3,5-Triaza-7-Phosphaadamantane Derivatives of Group 10 Metals, Including Metal Carbonyls and Hydrides

  摘要：

  The syntheses of Ni(PTA)(4) (5), Pd(PTA)(4) (6), and Pt(PTA)(4) (8) are accomplished through the reduction of the (MCl2)-Cl-II salts in water with excess 1,3,5-triaza-7-phosphaadamantane (PTA). The products are obtained as partially protonated derivatives with protonation occurring at the nitrogen atoms of the bound PTA ligands. Crystal structures illustrating the monoprotonated and bis-protonated derivatives of 8, [Pt(PTA)(3)(PTAH)][Cl] (1S) and [Pt(PTA)(2)](PTA)(3)[BF4](2) (2S), are reported. The crystal structure of an intermediate along the reduction pathway, [PdCl(PTA)(3)][Cl] (7), is also presented, showing a trans influence whereby the Pd-P bond length trans to the Cl- ligand is shorter, 2.238(3) Angstrom, than the average Pd-P bond length cis to the Cl- ligand, 2.334(2) Angstrom. Complex 8 is also protonated at the metal center to form [(H)Pt(PTA)(4)][X], where X = Cl-, BF4-, HCO3-, and C3H5CO2-, through the addition of weak acids such as CO2/H2O, NH4Cl, PTAH(+)Cl(-), HPy+BF4-, and crotonic acid. Addition of strong acids such as HCl or HBF4 results in protonation at the PTA ligands. Thereby, the Pt metal center is shown to have a pK(a) between 7.44 and 9.25. The bound PTA ligands on complex 8 have a pK(a) below 4.69 but above 2.12. Ni(CO)(4-n)(PTA)(n) derivatives are also reported for n = 3 (9), 2 (10), and 1 (11). Using LR data of 11, PTA is determined to have an electronic parameter (chi) as defined by Tolman to be 15.3 cm(-1), indicating PTA to be slightly less donating than PPh3, where chi = 12.8 cm(-1). Complex 10 is crystallized out of a MeOH/ether solution maintained at -15 degrees C and characterized by X-ray crystallography. It is a distorted tetrahedron and has a crystallographically determined Tolman cone angle of PTA of 103 degrees. Monitored reactions of Ni(PTA)(4) with CO in water via in situ IR techniques show that the rate observed for the dissociation of PTA to provide Ni(CO)(PTA)(3) is 7.92 x 10(-4) s(-1) at 20 degrees C. This rate, along with P-31 NMR results, indicates that the M-0(TA)(4) complexes exhibit little dissociation and slow exchange of the bound PTA ligands.

  DOI：

  10.1021/ic981243j