(mesityl)2BP(mesityl)2 | 136006-14-9

• 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: (mesityl)2BP(mesityl)2
• 英文别名: (dimesitylphosphino)dimesitylborane；Bis(2,4,6-trimethylphenyl)boranyl-bis(2,4,6-trimethylphenyl)phosphane；bis(2,4,6-trimethylphenyl)boranyl-bis(2,4,6-trimethylphenyl)phosphane
• CAS: 136006-14-9
• 化学式: C₃₆H₄₄BP
• 分子量: 518.53
• InChiKey: AIPYWWULWXUCGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.63
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  二(2,4,6-三甲基苯基)膦 、 二(三甲苯基)氟化硼 在 n-BuLi 作用下， 以 正己烷 为溶剂， 以36.3%的产率得到(mesityl)2BP(mesityl)2
  参考文献：
  名称：

  Nature of the boron-phosphorus bond in monomeric phosphinoboranes and related compounds

  摘要：

  The nature of the bonding between boron and phosphorus in monomeric phosphinoboranes (also called borylphosphanes, i.e., R2BPR2, R and R' = hydrocarbyl groups, B and P three-coordinate) and related species has been studied in some detail. This was accomplished by the synthesis and detailed spectroscopic and structural characterization of a number of rare monomeric phosphinoboranes and related derivatives. These compounds are distinguished by the presence of B-P moieties in which there is a lone pair located on phosphorus adjacent to an empty boron p-orbital. The main conclusion of these studies in that there exist fundamental differences between the B-P compounds and their B-N analogues. The major reason for this is the presence of a large inversion barrier at the phosphorus center, rather than any inherent weakness in B-P pi-bonds. The inversion barrier and the strength of the B-P pi-interaction can be controlled by electronic and steric factors. In essence, increasing the size and the electropositive character of the phosphorus substituents increases the strength of the B-P pi-bond. The compounds studied include Mes2BP(1-Ad)H, 1; Mes2BPPh2, 2; Mes2BP(t-Bu)2, 3; Mes2BPMes2, 4; Mes2BP(1-Ad)Li(Et2O)2, 5; Mes2BP(Ph)Li(Et2O), 6; (Mes2B)2PPh, 7; Mes2BP(1-Ad)PPh2, 8; Mes2BP(Ph)SiPh3, 9; and Mes2BP(1-Ad)SiMe3, 10 (Mes = 2,4,6-Me3C6H2, 1-Ad = 1-adamantanyl). They were examined by variable-temperature H-1, B-11, and P-31 NMR spectroscopy. Most compounds were also characterized by X-ray crystallography. The studies demonstrate that whereas the boron center is always planar, the phosphorus coordination can exhibit considerable geometrical variation between planarity and pyramidicity. There is a good correlation between the degree of pyramidicity at phosphorus and the B-P bond length, which can vary from 1.810 (4) angstrom for planar phosphorus to 1.948 (3) angstrom in the most pyramidal species. Variable-temperature H-1 NMR data for 1-3 and 10 reveal inversion barriers of < 12.4, < 10.4, and < 9.7 kcal mol-1 for 1, 2, and 10, whereas in the almost planar tert-butyl derivative 3 no dynamic behavior was observed as low as -97-degrees-C. Rotational barriers of 12.4 and 16.9 kcal mol-1 were also found for 1 and 10. The H-1 NMR data for the compounds 5-9, which have essentially planar geometry at phosphorus, afford rotational barriers (kcal mol-1) for the B-P multiple bond of 22.3 for 5, 22.2 for 6, 21.3 for 7, 21.3 for 8, and 17.1 for 9. In summary, it may be concluded that B-P pi-bonds are comparable in strength to B-N pi-bonds. Crystal data with Mo K-alpha radiation (lambda = 0.71069 angstrom) at 130 K: 1, C28H38BP, monoclinic, P2(1)/c, a = 9.461 (2) angstrom, b = 26.235 (10) angstrom, c = 10.415 (3) angstrom, beta = 111.93 (2)-degrees, R(3097 I > 3-sigma(I) data) = 0.050; 3, C26H40BP, monoclinic P2(1)/c, a = 23.530 (9) angstrom, b = 12.392 (5) angstrom, c = 18.119 (8) angstrom, beta = 110.88 (3)-degrees, R(3778I > 3-sigma(I) data) = 0.077; 4, C36H44BP, monoclinic, P2/n, a = 12.342 (4) angstrom, b = 7.703 (2) angstrom, c = 17.021 (5) angstrom, beta = 108.94 (2)-degrees, R(1973I > 2-sigma(I) data) = 0.059; 5, C40H67O3BPLi, monoclinic, P2(1)/n, a = 11.570 (2) angstrom, b = 20.203 (4) angstrom, c = 16.053 (5) anstrom, beta = 95.84 (2)-degrees, R(2595I > 3-sigma(I) data) = 0.065; 9, C42H42BPSi, triclinic, P1BAR, a = 9.112 (4) angstrom, b = 10.042 (6) angstrom, c = 19.479 (12) angstrom, alpha = 92.88 (5)-degrees, beta = 97.58 (5)-degrees, gamma = 97.03 (4)-degrees, R(4180I > 3-sigma(I) data) = 0.081; 10, C31H46BPSi, orthorhombic, P2(1)P2(1)P2(1), a = 9.625 (5) angstrom, b = 11.067 (6) angstrom, c = 26.676 (12) angstrom, R(1958I > 2-sigma(I) data) = 0.056.

  DOI：

  10.1021/ja00022a034

文献信息

• Nature of the boron-phosphorus bond in monomeric phosphinoboranes and related compounds
  作者：Doris C. Pestana、Philip P. Power

  DOI：10.1021/ja00022a034

  日期：1991.10

  The nature of the bonding between boron and phosphorus in monomeric phosphinoboranes (also called borylphosphanes, i.e., R2BPR2, R and R' = hydrocarbyl groups, B and P three-coordinate) and related species has been studied in some detail. This was accomplished by the synthesis and detailed spectroscopic and structural characterization of a number of rare monomeric phosphinoboranes and related derivatives. These compounds are distinguished by the presence of B-P moieties in which there is a lone pair located on phosphorus adjacent to an empty boron p-orbital. The main conclusion of these studies in that there exist fundamental differences between the B-P compounds and their B-N analogues. The major reason for this is the presence of a large inversion barrier at the phosphorus center, rather than any inherent weakness in B-P pi-bonds. The inversion barrier and the strength of the B-P pi-interaction can be controlled by electronic and steric factors. In essence, increasing the size and the electropositive character of the phosphorus substituents increases the strength of the B-P pi-bond. The compounds studied include Mes2BP(1-Ad)H, 1; Mes2BPPh2, 2; Mes2BP(t-Bu)2, 3; Mes2BPMes2, 4; Mes2BP(1-Ad)Li(Et2O)2, 5; Mes2BP(Ph)Li(Et2O), 6; (Mes2B)2PPh, 7; Mes2BP(1-Ad)PPh2, 8; Mes2BP(Ph)SiPh3, 9; and Mes2BP(1-Ad)SiMe3, 10 (Mes = 2,4,6-Me3C6H2, 1-Ad = 1-adamantanyl). They were examined by variable-temperature H-1, B-11, and P-31 NMR spectroscopy. Most compounds were also characterized by X-ray crystallography. The studies demonstrate that whereas the boron center is always planar, the phosphorus coordination can exhibit considerable geometrical variation between planarity and pyramidicity. There is a good correlation between the degree of pyramidicity at phosphorus and the B-P bond length, which can vary from 1.810 (4) angstrom for planar phosphorus to 1.948 (3) angstrom in the most pyramidal species. Variable-temperature H-1 NMR data for 1-3 and 10 reveal inversion barriers of < 12.4, < 10.4, and < 9.7 kcal mol-1 for 1, 2, and 10, whereas in the almost planar tert-butyl derivative 3 no dynamic behavior was observed as low as -97-degrees-C. Rotational barriers of 12.4 and 16.9 kcal mol-1 were also found for 1 and 10. The H-1 NMR data for the compounds 5-9, which have essentially planar geometry at phosphorus, afford rotational barriers (kcal mol-1) for the B-P multiple bond of 22.3 for 5, 22.2 for 6, 21.3 for 7, 21.3 for 8, and 17.1 for 9. In summary, it may be concluded that B-P pi-bonds are comparable in strength to B-N pi-bonds. Crystal data with Mo K-alpha radiation (lambda = 0.71069 angstrom) at 130 K: 1, C28H38BP, monoclinic, P2(1)/c, a = 9.461 (2) angstrom, b = 26.235 (10) angstrom, c = 10.415 (3) angstrom, beta = 111.93 (2)-degrees, R(3097 I > 3-sigma(I) data) = 0.050; 3, C26H40BP, monoclinic P2(1)/c, a = 23.530 (9) angstrom, b = 12.392 (5) angstrom, c = 18.119 (8) angstrom, beta = 110.88 (3)-degrees, R(3778I > 3-sigma(I) data) = 0.077; 4, C36H44BP, monoclinic, P2/n, a = 12.342 (4) angstrom, b = 7.703 (2) angstrom, c = 17.021 (5) angstrom, beta = 108.94 (2)-degrees, R(1973I > 2-sigma(I) data) = 0.059; 5, C40H67O3BPLi, monoclinic, P2(1)/n, a = 11.570 (2) angstrom, b = 20.203 (4) angstrom, c = 16.053 (5) anstrom, beta = 95.84 (2)-degrees, R(2595I > 3-sigma(I) data) = 0.065; 9, C42H42BPSi, triclinic, P1BAR, a = 9.112 (4) angstrom, b = 10.042 (6) angstrom, c = 19.479 (12) angstrom, alpha = 92.88 (5)-degrees, beta = 97.58 (5)-degrees, gamma = 97.03 (4)-degrees, R(4180I > 3-sigma(I) data) = 0.081; 10, C31H46BPSi, orthorhombic, P2(1)P2(1)P2(1), a = 9.625 (5) angstrom, b = 11.067 (6) angstrom, c = 26.676 (12) angstrom, R(1958I > 2-sigma(I) data) = 0.056.