(hydrotris(3,5-dimethyl-1-pyrazolyl)borate)Ni-S-2,6-Ph2C6H3 | 1204315-08-1

• 英文名称: (hydrotris(3,5-dimethyl-1-pyrazolyl)borate)Ni-S-2,6-Ph2C6H3
• CAS: 1204315-08-1
• 化学式: C₃₃H₃₅BN₆NiS
• 分子量: 617.248
• InChiKey: QPIHHGDNXYYTBF-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  sodium-2,6-diphenylthiophenolate 、 chloro(2,2,2-κ3-hydridotris(3,5-dimethylpyrazolyl)borate)nickel(II) 以 四氢呋喃 为溶剂， 生成 (hydrotris(3,5-dimethyl-1-pyrazolyl)borate)Ni-S-2,6-Ph2C6H3
  参考文献：
  名称：

  Steric Titration of Arylthiolate Coordination Modes at Pseudotetrahedral Nickel(II) Centers

  摘要：

  Several derivatives of the pseudotetrahedral phenylthiolate complex Tp(Me,Me) Ni-SPh (1), Tp(Me,Me-) = hydrotris(3,5-dimethyl-1-pyrazolyl) borate, were prepared incorporating substituted arylthiolates, including a series of orthosubstituted ligands Tp(Me,Me)Ni-SR (R = 2,6-Me(2)C(6)H(3), 2: 2,4,6-Me(3)C(6)H(2), 3; 2,4,6- (i)Pr(3)C(6)H(2), 4; and 2,6-Ph(2)C(6)H(3), 5) and a series of para-substituted complexes (R = C(6)H(4)-4-OMe, 6; C(6)H(4)-4-Me, 7; and C(6)H(4)-4-Cl, 8). The products were characterized by (1)H NMR and UV-vis spectroscopy. Spectra of 6-8 were consistent with retention of a common structure across the para-substituted series with modest perturbation of the spectral features of 1 assisting their assignment. In contrast, spectra of 2-5 were indicative of a significant change in configuration across the ortho-disubstituted series. The structure of complex 5 was determined by X-ray crystallography and a distinctive arylthiolate ligation mode was found, in which the N(3)S ligand field was significantly distorted toward a sawhorse, compared to a more common trigonal pyramidal shape (e.g., 1). Moreover, the arylthiolate substituent rotated from a vertical orientation co-directional with the pyrazole rings and disposed between two of them in 1, to a horizontal orientation perpendicular to and over a single pyrazole ring in 5. This reorientation is necessary to accommodate the large ortho substituents of the latter complex. The divergent Ni-S coordination modes result in distinct (1)H NMR and electronic spectra that were rationalized by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. These results demonstrate rich coordination chemistry for arylthiolates that can be elicited by steric manipulation at the periphery of pseudotetrahedral ligand fields.

  DOI：

  10.1021/ic901347p