tri(p-tolyl)bromogermane | 72454-26-3

• 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: tri(p-tolyl)bromogermane
• 英文别名: [(p-tolyl)3(germanium)bromide]；[Tol3GeBr]；Bromotris(4-methylphenyl)germane；bromo-tris(4-methylphenyl)germane
• CAS: 72454-26-3
• 化学式: C₂₁H₂₁BrGe
• 分子量: 425.892
• InChiKey: RLTVWVAZMUNXAV-UHFFFAOYSA-N

物化性质

• 熔点：
  127-128 °C
• 沸点：
  442.3±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tri(p-tolyl)bromogermane 、 triphenylplumbyllithium 以 四氢呋喃 、 乙醚 为溶剂， 以26%的产率得到Tri-p-tolyl(triphenylplumbyl)germane
  参考文献：
  名称：

  On Mixed Group 14-Group 14 Bonds. 8. Asymmetrically Substituted Compounds Ar3PbGeAr'3 and Ar3PbPbAr'3: Comparison of Structure and Physical Behavior in the Series of Bonds Sn-Sn, Pb-Ge, Pb-Sn, and Pb-Pb

  摘要：

  A general procedure for the synthesis of hexaarylated compounds of the type Ar3PbGeAr's from Ar3PbLi and Ar'3GeX in THF/ether at -60-degrees-C is given. Likewise, from Ar3PbLi and Ar'PbI the asymmetrical diplumbanes Ar3PbPbAr3 could be prepared. By the use of the bulky groups Ar and Ar', the migration of aryl groups could be suppressed, avoiding the appearance of the mixtures Pb2Ar6-nAr'n (n = 0-6). Nonetheless, the resulting diplumbanes Ar3Pb-PbAr'3 were always partially contaminated with some symmetric Pb2Ar6 and Pb2Ar'6. The structures of (p-Tol)3PbGePh3 (triclinic, space group P1BAR; a = 9.983(1) b = 12.201(1) c = 15.728(2) angstrom; alpha = 95.73(1), beta = 103.56(1), gamma = 113.06(1)degrees; V = 1674(1) angstrom3; Z = 2; R = 0.0434) and (p-Tol)3PbGe-(p-Tol)3 (trigonal, space group R3BAR; a = 13.338(1), c = 36.55(1) angstrom; V = 5631(2) angstrom3; Z = 6; R = 0.0522) have been determined. NMR chemical shifts delta(Sn-119) and delta(Pb-207) (40 compounds) and one-bond couplings 1J(M-M') (16 compounds), stretching vibrations nu(M-M') and force constants f(M-M') for a diatomic oscillator (38 compounds), and bond distances d(M-M') (18 compounds) are compared for all six combinations M/M' = Ge/Sn/Pb of Ar3M-M'Ar'3. Concerning the asymmetric diplumbanes Ar3Pb-PbAr'3, assignments of delta(Pb-207) resulted from a consideration of inductivity (comparison to PbAr4/Ar'4) and an assumed order of charge flow DELTA(Ar <-> Ar') (13 compounds). Sequences exist for delta(Sn-119) (Pb-Sn > Sn-Sn greater-than-or-equal-to Sn-Ge), delta(Pb-207) (Pb-Pb > Pb-Sn almost-equal-to Pb-Ge), f (Sn-Ge > Sn-Sn greater-than-or-equal-to Pb-Sn, and Pb-Ge > Pb-Sn greater-than-or-equal-to Pb-Pb), d (Sn-Ge less-than-or-equal-to Pb-Ge < Sn-Sn less-than-or-equal-to Pb-Sn less-than-or-equal-to Pb-Pb) and reduced spin-spin couplings 1K (Pb-Sn > Sn-Sn > Pb-Pb ''scatter''). The polarities Pb(delta-)-Ge(delta+) and Pb(delta-)-Sn(delta+) are obvious. The enhanced electronegativity of lead demonstrates the influence of its relativistically contracted 6s and 6p orbitals. With regard to Ar3Pb-PbAr'3, a relation between 1K(Pb-Pb) and the charge flow DELTA(Ar <-> Ar') is indicated.

  DOI：

  10.1021/om00019a033
• 作为产物：
  描述：

  (Trisulfane-1,3-diyl)bis[tris(4-methylphenyl)germane] 、 二溴三苯基膦 以 二氯甲烷 为溶剂， 以>99的产率得到tri(p-tolyl)bromogermane
  参考文献：
  名称：

  Molecular sulfur (S2): generation and synthetic application

  摘要：

  DOI：

  10.1021/ja00315a061

文献信息

• Tetraaryl-methane analogues in group 14-4. Ph4−nM(p-Tol)n (n = 0–4, M = Si, Ge, Sn, Pb). Synthesis, structural and spectroscopic data, and semi empirical calculations: Mutual interaction of tetrahedral σ-orbitals (symmetry and electronegativity) and delocalized σ-lumos (π-Lewis acidity)
  作者：Michael Charissé、Bernd Mathiasch、Martin Dräger、Umberto Russo

  DOI：10.1016/0277-5387(95)00069-5

  日期：1995.8

  been synthesized by lithium (M = Si) or Grignard methods (M = Ge, Sn, Pb). The crystal structure of Ph 3 Sn( p -Tol), a survey of the 10 known structures and spectroscopic data (NMR, Mossbauer, IR, Raman) are given. A change of the symmetry of the formally tetrahedral MC 4 backbone arises if M = Si and Ge (elongation along one S 4 or C 3 axis) are altered to M = Sn and Pb (contraction along one S 4 axis)

  摘要标题中提到的20种化合物是通过锂（M = Si）或格利雅（Grignard）方法（M = Ge，Sn，Pb）合成的。给出了Ph 3 Sn（p -Tol）的晶体结构，十种已知结构的调查以及光谱数据（NMR，Mossbauer，IR，Raman）。如果将M = Si和Ge（沿一个S 4或C 3轴的伸长率）更改为M = Sn和Pb（沿一个S 4轴的收缩率），则会出现形式上为四面体MC 4骨架对称性的变化。δ（13 C-ipso）的阶数表示沿Pb⪢Sn> Ge> Si的电负性降低。29 Si，119 Sn和207 Pb NMR化学位移沿每个系列显示“下垂”，用二次方程式进行分析描述。该方程式的线性部分被解释为电感性贡献，如果M从硅变为锡和铅，则电感性贡献会改变其符号。二次部分反映了低层LUMO的不同族群，其电荷由芳族基团提供。LUMO在硅的情况下略微抗粘结，而在锡和铅的情况下微弱粘结。M的“π受体”性质解释了与MAlkyl
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ge: SVol., 128, page 554 - 556
  作者：

  DOI：——

  日期：——
• Some Tolyl Derivatives of Germanium¹
  作者：J. K. Simons、E. C. Wagner、J. H. Müller

  DOI：10.1021/ja01336a037

  日期：1933.9
• On Mixed Group 14-Group 14 Bonds. 8. Asymmetrically Substituted Compounds Ar3PbGeAr'3 and Ar3PbPbAr'3: Comparison of Structure and Physical Behavior in the Series of Bonds Sn-Sn, Pb-Ge, Pb-Sn, and Pb-Pb
  作者：Hans-Juergen Koglin、Kerstin Behrends、Martin Draeger

  DOI：10.1021/om00019a033

  日期：1994.7

  A general procedure for the synthesis of hexaarylated compounds of the type Ar3PbGeAr's from Ar3PbLi and Ar'3GeX in THF/ether at -60-degrees-C is given. Likewise, from Ar3PbLi and Ar'PbI the asymmetrical diplumbanes Ar3PbPbAr3 could be prepared. By the use of the bulky groups Ar and Ar', the migration of aryl groups could be suppressed, avoiding the appearance of the mixtures Pb2Ar6-nAr'n (n = 0-6). Nonetheless, the resulting diplumbanes Ar3Pb-PbAr'3 were always partially contaminated with some symmetric Pb2Ar6 and Pb2Ar'6. The structures of (p-Tol)3PbGePh3 (triclinic, space group P1BAR; a = 9.983(1) b = 12.201(1) c = 15.728(2) angstrom; alpha = 95.73(1), beta = 103.56(1), gamma = 113.06(1)degrees; V = 1674(1) angstrom3; Z = 2; R = 0.0434) and (p-Tol)3PbGe-(p-Tol)3 (trigonal, space group R3BAR; a = 13.338(1), c = 36.55(1) angstrom; V = 5631(2) angstrom3; Z = 6; R = 0.0522) have been determined. NMR chemical shifts delta(Sn-119) and delta(Pb-207) (40 compounds) and one-bond couplings 1J(M-M') (16 compounds), stretching vibrations nu(M-M') and force constants f(M-M') for a diatomic oscillator (38 compounds), and bond distances d(M-M') (18 compounds) are compared for all six combinations M/M' = Ge/Sn/Pb of Ar3M-M'Ar'3. Concerning the asymmetric diplumbanes Ar3Pb-PbAr'3, assignments of delta(Pb-207) resulted from a consideration of inductivity (comparison to PbAr4/Ar'4) and an assumed order of charge flow DELTA(Ar <-> Ar') (13 compounds). Sequences exist for delta(Sn-119) (Pb-Sn > Sn-Sn greater-than-or-equal-to Sn-Ge), delta(Pb-207) (Pb-Pb > Pb-Sn almost-equal-to Pb-Ge), f (Sn-Ge > Sn-Sn greater-than-or-equal-to Pb-Sn, and Pb-Ge > Pb-Sn greater-than-or-equal-to Pb-Pb), d (Sn-Ge less-than-or-equal-to Pb-Ge < Sn-Sn less-than-or-equal-to Pb-Sn less-than-or-equal-to Pb-Pb) and reduced spin-spin couplings 1K (Pb-Sn > Sn-Sn > Pb-Pb ''scatter''). The polarities Pb(delta-)-Ge(delta+) and Pb(delta-)-Sn(delta+) are obvious. The enhanced electronegativity of lead demonstrates the influence of its relativistically contracted 6s and 6p orbitals. With regard to Ar3Pb-PbAr'3, a relation between 1K(Pb-Pb) and the charge flow DELTA(Ar <-> Ar') is indicated.
• Molecular sulfur (S2): generation and synthetic application
  作者：Kosta Steliou、Yves Gareau、David N. Harpp

  DOI：10.1021/ja00315a061

  日期：1984.2