lithium 1-methylboratabenzene | 160298-02-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: lithium 1-methylboratabenzene
• 英文别名: Lithium;1-methyl-1-boranuidacyclohexa-1,3,5-triene
• CAS: 160298-02-2
• 化学式: C₆H₈B*Li
• 分子量: 97.8815
• InChiKey: MSJMDZQEDLSOHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.75
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium 1-methylboratabenzene 、 氯化铪 以 甲苯 为溶剂， 以60%的产率得到dichlorobis(1-methylboratabenzene)hafnium
  参考文献：
  名称：

  硼苯衍生物。26. 1钛，锆和Ha的1-甲基硼烷苯配合物的合成。TiCl 3（C 5 H 5 BMe），TiCl 2 Cp（C 5 H 5 BMe），ZrCl 2（C 5 H 5 BMe）2和ZrCl 2 Cp *（C 5 H 5 BMe）的结构†

  摘要：

  TiCl 3（C 5 H 5 BMe）（6a），[MCl 3（C 5 H 5 BMe）] x（6b，M = Zr; 6c，M = Hf）和MCl 2（C 5 H 5 BMe） ）2（7b，M = Zr; 7c，M = Hf）由四氯化物MCl 4（M = Ti，Zr，Hf）和Li（C 5 H 5 BMe）（3），2-（Me 3 Si C 5 H 5 BMe（4）或2-（Me 3 Sn）C 5 H 5 BMe（5）的高收率。MCl 2 Cp（C 5 H 5 BMe）（8a，M = Ti; 8b，M = Zr）和MCl 2 Cp *（C 5 H 5 BMe）（9b，M = Zr; 9c，M = Hf）的配合物由相应的环戊二烯基前体MCl 3 Cp（M = Ti，Zr）和MCl 3 Cp *（M = Zr，Hf）相似地制备。氧化还原电势比对应的Cp络合物移动了0.35-0.41 V，以产生更多的阳

  DOI：

  10.1021/om970313b
• 作为产物：
  描述：

  trimethylaluminium dimer 、 Lithium;oxolane;2,2,3,3-tetramethyl-1,4-dioxa-5-boranuidaspiro[4.5]deca-6,8-diene 以 乙醚 、 甲苯 为溶剂， 以79%的产率得到lithium 1-methylboratabenzene
  参考文献：
  名称：

  Borabenzene Derivatives. 22. Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe]

  摘要：

  Borylation of potassium pentadienide with BCl(NR(2))(2) and subsequent alcoholysis produce 2,4-pentadienylboranes C5H7B(NR(2))(2) (4a-c: R = Me, Et, Pr-i), C5H7B(OR)(2) (4e,f: R = Et, Bu(t)), and C5H7B(OCR(2))(2) with 1,3,2-dioxaborolane rings (4g,h: R = H, Me) as mixtures of E and Z isomers. Metalation of 4a,b in THF by lithium dialkylamides LiNR'(2) (R' = Me, Et, Pr-i) in the presence of TMEDA. results fi) in a nonproductive deborylation via primary attack at the boron center, (ii) in ring closure to produce boratabenzene salts [Li(TMEDA)][C5H5-BNR(2)] (10a,b: R = Me, Et), and (iii) in substitution of B-dialkylamino groups when NR(2) is bulkier than NR'(2). 10a is obtained in 26.5% yield. Metalation of 4h in THF by the sterically demanding lithium dialkylamides LDA and LiTMP affords a precipitate of the spiroborate [Li(THF][C5H6B(OCMe(2))(2)] (13) in 63% yield in equilibrium with the presumed isomer Li-[C5H5BO(CMe(2))(2)OH] (Li(Sg)) in the THF solution. 13 can be transformed into boratabenzenes by several methods. (i) Treatment with Me(3)SiCl produces a 1:1 mixture of isomeric boracyclohexadienes C(5)H(6)BOCMe(2)CMe(2)OSiMe(3) (15a, 2,4-isomer; 15b, 2,5-isomer) which, on subsequent low-temperature metalation, give Li[C5H5BO(CMe(2))OSiMe(3)] (Li(3h)). (ii) Metalation of 13 at -78 degrees C affords Li-2[C5H5BO(CMe(2))O] (Li-2(3i)) and, after treatment with Me(3)SiCl, the bora-2,4-cyclohexadiene (5-Me(3)Si)C(5)H(5)BOCMe(2)CMe(2)OSiMe(3) (16). (iii) Treatment of 13 with Al(2)Me(6) in toluene at -78 degrees C affords Li[C(5)H(5)BMe] (Li(3b)) in 79% yield as a white solid. This salt is also obtained from Li(3h) and Al(2)Me(6). (iv) Addition of 15 to LiBu(t) in pentane/hexane produces Li[C(5)H(5)BBu(t)] (Li(3c)) in 53% yield. Combining strongly alkaline aqueous solutions of[NMe(3)Ph]I and Li(3b) affords [NMe(3)Ph][C(5)H(5)BMe] (18). 18 crystallizes in the monoclinic space group P2(1)/n with a = 935.4(1) pm, b = 1557.4(4) pm, c = 988.8(1) pm, beta = 95.47(1)degrees, and Z = 4. The 1-methylboratabenzene ion of 18 displays nearly perfect C-2 nu symmetry with intra-ring bond distances of 150.1, 138.8, and 139.2 pm (average) for B-C1 (B-C5), C1-C2 (C4-C5), and C2-C3 (C3-C4), respectively.

  DOI：

  10.1021/om00001a064

文献信息

• Synthesis, Characterization, and Reactivity of Chromium Boratabenzene Complexes
  作者：Jonathan S. Rogers、Xianhui Bu、Guillermo C. Bazan

  DOI：10.1021/om0003685

  日期：2000.9.1

  to the reactivity observed with the isoelectronic cyclopentadienyl salts, the reaction of CrCl3(THF)3 with boratabenzene anions results in the formation of Cr(II) complexes. Thus, addition of Li(C5H5B−Me) to CrCl3(THF)3 in THF gives (C5H5B−Me)2Cr (3). Similarly, Li(C5H5B−NMe2) and CrCl3(THF)3 yield (C5H5B−NMe2)2Cr (4), while Li(C5H5B−Ph) and CrCl3(THF)3 provide (C5H5B−Ph)2Cr (5). Compounds 3−5 were characterized

  与等电子式环戊二烯基盐所观察到的反应性相反，CrCl 3（THF）3与硼酸苯阴离子的反应导致形成Cr（II）络合物。因此，将Li（C 5 H 5 B-Me）添加到THF中的CrCl 3（THF）3中，得到（C 5 H 5 B-Me）2 Cr（3）。同样，Li（C 5 H 5 B-NMe 2）和CrCl 3（THF）3产生（C 5 H 5 B-NMe 2）2 Cr（4），而Li（C 5 H 5 B-Ph）和CrCl 3（THF）3提供（C 5 H 5 B-Ph）2 Cr（5）。化合物3 - 5通过单晶X射线衍射研究进行表征，并都具有典型的夹层结构。硼苯-配体加合物与合适的Cr（III）原料的反应提供了硼苯-Cr（III）配合物。在苯中的MeCrCl 2（THF）3中添加C 5 H 5 B-PMe 3（Bb -PMe 3）得到（C 5H 5 B-Me）CrCl 2（PMe 3）（6）低产率。用硼烷的吡啶加合物C
• Three Conformational Polymorphs of Di-<i>μ</i>-chlorotetrakis(1-methylboratabenzene)diyttrium:  Synthesis, X-ray Structures, Quantum Chemical Calculations, and Lattice Energy Minimizations¹
  作者：Xiaolai Zheng、Bing Wang、Ulli Englert、Gerhard E. Herberich

  DOI：10.1021/ic0014641

  日期：2001.6.1

  calculations at the B3LYP/LanL2DZ level reveal that the three molecular structures observed in the solid state correspond closely to three minima on the gas-phase potential energy surface. The beta conformation is 2.8 and 7.2 kJ/mol more stable than the alpha and gamma conformations, respectively. Lattice energy minimizations predict that the alpha-1 phase is about 5.5 and 18.7 kJ mol(-)(1) more stable

  三氯化钇与1-甲基硼酸锂（1/2）在甲苯中的反应（110摄氏度，3天）得到了无供体的双核夹心复合物[（C（5）H（5）BMe）（2）Y（ mu-Cl）]（2）（1）的产率为85％，为淡黄色晶体。通过单晶和粉末衍射法，三个构象多晶型，α-1[P2（1）/ n（No. 14），单斜晶，a = 6.6124（8）A，b = 14.352（9）A，c = 14.120（1）A，β= 95.57（1）度，V = 1333.7（9）A（3），Z = 2]，β-1[P2（1）/ a（No. 14），单斜，a = 8.542（2）A，b = 13.712（6）A，c = 11.76（1）A，β= 102.60（4）度，V = 1344.5（13）A（3），Z = 2]和gamma-1 [Pbca（No. 61），斜方晶，a = 20.091（5）A，b = 13.527（3）A，c = 9.976（2）A，V
• Borabenzene Derivatives. 24.¹ From Lithium 1-Methylboratabenzene to 2-Mono- and 2,2-Disubstituted 1-Methyl-1,2-dihydroborinines with Me₃Si, Me₃Ge, Me₃Sn, and Me₃Pb Substituents. Degenerate Sigmatropic Rearrangements with Exceptionally Low Barriers and the Structure of 2-(Me₃Sn)C₅H₅BMe
  作者：Gerhard E. Herberich、Jörg Rosenplänter、Bernd Schmidt、Ulli Englert

  DOI：10.1021/om9605701

  日期：1997.3.1

  ΔH⧧ = 43.3(6) kJ mol-1, and ΔS⧧ = −52(2) J K-1 mol-1; for 3 ΔG300⧧ = 43.4(9) kJ mol-1, ΔH⧧ = 27.8(3) kJ mol-1, and ΔS⧧ = −52(2) J K-1 mol-1] and are lower than those found for previously investigated systems. The Sn and Pb satellites observed for 4 and 5 in THF solutions are quenched by catalytic amounts of DMSO while chemical shifts are not affected even at higher concentrations. The Si compound 2

  Li（C 5 H 5 BMe）（1）与亲电子体Me 3 ECl（E = Si，Ge，Sn，Pb）的反应生成1,2-二氢硼烷酮2-（Me 3 E）C 5 H 5 BMe（2 − 5）。Sn化合物4的结构显示出延长的Sn-C（环）键[228.7（2）pm]。在溶液中的化合物2 - 5是fluxional并显示[1,3]所述的Meσ迁移迁移3从C-2] E组至C-6。通过NMR光谱已经确定了2和3的简并σ重排的障碍[对于2 Δ ģ 300 ⧧ = 58.9（11）千焦摩尔-1，Δ ħ ⧧ = 43.3（6）千焦摩尔-1，Δ小号⧧ = -52（2）JK -1摩尔-1 ; 为3 Δ ģ 300 ⧧ = 43.4（9）千焦摩尔-1，Δ ħ ⧧ = 27.8（3）千焦摩尔-1，Δ小号⧧ = -52（2）JK -1摩尔-1 ]，并且低于为先前研究的系统找到的那些。在4和5观测到的Sn和Pb卫星通过催化量的
• Boratatrozircenes: cycloheptatrienyl zirconium boratabenzene sandwich complexes – evaluation of potential η6–η5 hapticity interconversions
  作者：Andreas Glöckner、Peng Cui、Yaofeng Chen、Constantin G. Daniliuc、Peter G. Jones、Matthias Tamm

  DOI：10.1039/c2nj40059f

  日期：——

  The salt metathesis reactions of [(η7-C7H7)ZrCl(tmeda)] (1) with various boratabenzene ligands Li(C5H5B–R) (R = H, CH3, CC–SiMe3) afford the 16-electron sandwich complexes [(η7-C7H7)Zr(η6-C5H5B–R)] (2: R = H, 3: R = CH3, 4: R = CC–SiMe3). The molecular structures of 3 and 4 were determined by X-ray diffraction analyses; they display distorted η6-coordinated boratabenzene ligands with short Zr–B bonds of 2.683(2) and 2.649(6) Å. The possibility of an η6–η5 hapticity interconversion, accompanied by B–L bond formation, upon addition of a Lewis base L (L = PMe3, 4-(dimethylamino)-pyridine) to 3 was studied. However, Zr–L bond formation was observed instead, leading to [(η7-C7H7)Zr(η6-C5H5B–CH3)(L)] (5: L = PMe3, 6: L = 4-(dimethylamino)-pyridine), even if a large excess of L was used.

  [(δ-7-C7H7)ZrCl(tmeda)]（1）与各种硼烷配体 Li(C5H5BâR)（R = H、CH3、CCâSiMe3）的盐元合成反应生成了 16 电子夹层配合物[(δ-7-C7H7)Zr(δ-6-C5H5BâR)]（2：R = H；3：R = CH3；4：R = CCâSiMe3）。通过 X 射线衍射分析确定了 3 和 4 的分子结构；它们显示了畸变的δ-6 配位硼苯配体，其 ZrâB 短键分别为 2.683(2) 和 2.649(6) Ã。研究人员研究了在 3 中加入路易斯碱 L（L = PMe3，4-（二甲基氨基）-吡啶）后发生δ-6δ-5 触变的可能性以及 BâL 键的形成。然而，即使使用了大量过量的 L，也没有观察到 ZrâL 键的形成，而是形成了[(δ-7-C7H7)Zr(δ-6-C5H5BâCH3)(L)]（5: L = PMe3，6: L = 4-（二甲基氨基）-吡啶）。
• Borabenzene Derivatives. 29. Synthesis and Structural Diversity of Bis(boratabenzene)scandium Complexes. Structures of [ScCl(C₅H₅BMe)₂]₂, [ScCl(3,5-Me₂C₅H₃BNMe₂)₂]₂, and ScCl[3,5-Me₂C₅H₃BN(SiMe₃)₂]₂¹
  作者：Gerhard E. Herberich、Ulli Englert、Andreas Fischer、Jiahong Ni、Andreas Schmitz

  DOI：10.1021/om990548i

  日期：1999.12.1

  The bis(boratabenzene)scandium complexes 3-5 are synthesized from solvent-free lithium boratabenzenes and ScCl3 in toluene (110 degrees C, 3 days). Complex [ScCl(C5H5BMe)(2)](2) (3) possesses a doubly chloro-bridged dinuclear structure with four facially coordinated boratabenzene ligands. Compound [ScCl(3,5-Me2C5H3BNMe2)(2)](2) (4) differs from 3 in that each scandium atom binds to one boratabenzene in an unprecedented N-B-C-2 coordination mode and facially to the second boratabenzene ligand; in solution 4 is fluxional, displaying only one type of boratabenzene ligand with effective lateral symmetry. Complex ScCl[3,5-Me2C5H3BN(SiMe3)(2)](2) (5) is mononuclear because of the bulkiness of its boratabenzene. Metalation of the 1,2,3,6-tetrahydroborinine 3-CH2-5-MeC5H5BNMe2 (9) affords the solvent-free boratabenzene Li(3,5-Me2C5H3BNMe2) (7). The mixture of 1,2- and 1,4-dihydroborines 3,5-Me2C5H4BNMe2 (10a,b) (accessible from 9 by isomerization) can be transformed into the solvent-free boratabenzene Li[3,5-Me2C5H3BN(SiMe3)(2)] (8) by (i) treatment with BCl3 to give the chloro derivatives 11a,b, (ii) subsequent amination with NH(SiMe3)(2)/NEt3, and (iii) metalation with LiN(SiMe3)(2).