3,4-dimethyl-1-phenyl-3-borolene | 112238-06-9

• 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: 3,4-dimethyl-1-phenyl-3-borolene
• 英文别名: 3,4-Dimethyl-1-phenyl-2,5-dihydro-1H-borole；3,4-dimethyl-1-phenyl-2,5-dihydroborole
• CAS: 112238-06-9
• 化学式: C₁₂H₁₅B
• 分子量: 170.062
• InChiKey: RJEWGMKPLOLPAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• 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

• 作为反应物：
  描述：

  3,4-dimethyl-1-phenyl-3-borolene 在 锌 作用下， 以 乙醚 为溶剂， 以84%的产率得到4-Isopropenyl-5-isopropylidene-4-methyl-2-phenyl-[1,2]oxaborolane
  参考文献：
  名称：

  Herberich, Gerhard E.; Englert, Ulli; Wang, Shaotian, Chemische Berichte, 1993, vol. 126, # 2, p. 297 - 304

  摘要：

  DOI：
• 作为产物：
  描述：

  二氯苯酚溴酯 、 2,3-二甲基-1,3-丁二烯 在 Mg 作用下， 以 正戊烷 为溶剂， 以34%的产率得到3,4-dimethyl-1-phenyl-3-borolene
  参考文献：
  名称：

  Herberich, Gerhard E.; Marx, Hans-W.; Wagner, Trixie, Chemische Berichte, 1994, vol. 127, # 11, p. 2135 - 2140

  摘要：

  DOI：

文献信息

• Derivate des borols
  作者：G.E. Herberich、W. Boveleth、B. Hessner、M. Hostalek、D.P.J. Köffer、M. Negele

  DOI：10.1016/s0022-328x(00)99604-9

  日期：1987.1

  Dehydrogenating complexation of borolenes with carbonyls (Ru3(CO)12, Os3(CO)12), Wilkinson's catalyst (RhCl(PPh3)3) and related compounds (RuCl2(PPh3)3, RuHCl(PPh3)3, OSCl2(PPh3)3), and (η6-arene)ruthenium complexes (Ru(η-C6H6)(η4-C6H8), [Ru(η-C6H6)Cl2]2, [Ru(η-C6-Me6)Cl2]2) leads to the (η5-borole)metal complexes of Ru, Os, and Rh. Inter alia, the preparation of the complexes Ru(CO)3(η5-C4H4BF) (R

  硼烷与羰基（Ru 3（CO）12，OS 3（CO）12），威尔金森氏催化剂（RhCl（PPh 3）3）和相关化合物（RuCl 2（PPh 3）3，RuHCl（PPh 3）3）的脱氢络合，OSCL 2（PPH 3）3），和（η 6 -arene）钌络合物（茹（η-C 6 H ^ 6）（η 4 -C 6 ħ 8），的[Ru（η-C 6 H ^ 6）氯2个] 2，[茹（η-C 6 -Me 6）氯2 ] 2）通向（η 5钌，锇，和Rh的-borole）金属配合物。除其他外，配合物的Ru（CO）的制备3（η 5 -C 4 H ^ 4 BF）（R = PH，OME中，Me），OS（CO）3 L（L =η 5 -C 4 H ^ 4 BPH ），描述了MHClL（PPh 3）2（M ＝ Ru，OS），RhClL（PPh 3）2和RuL（η- C6 R 6）（R ＝ H，Me）。RuHClL（PPh 3的结构）2和RhClL（PPh
• Borole derivatives. 20. Three-center Fe-H-B bonding in (borole)(cyclopentadienyl)hydridoiron derivatives
  作者：Gerhard E. Herberich、Tobias Carstensen、Dieter P. J. Koeffer、Norbert Klaff、Roland Boese、Isabella Hyla-Kryspin、Rolf Gleiter、Martin Stephan、Helmut Meth、Ulrich Zenneck

  DOI：10.1021/om00014a037

  日期：1994.2

  (Borole)tricarbonyliron complexes Fe(CO)3(3,4-R1(2)C4H2BPh) (3a, R1 = H; 3b, R1 = Me) react with cyclopentadiene under irradiation to give the hydrides CpFeH(3,4-R1(2)C4H2BPh) (1a,b). Deprotonation by NaH in THF produces the borataferrocene anions [CpFe(3,4-R1(2)C4H2BPh)]-(5a-, 5b-). These can be alkylated in the 2-/5-position by alkyl iodides in the presence of NaH to give 2,5-dialkyl hydride derivatives: e.g. CpFeH(2,5-R2(2)C4H2BPh) (1c, R2 = Me; 1g, R2 = CH2=CH(CH2)4; 1h, R2 = (CH2)2CHCH2). The structures of CpFeH(2,3,4,5-Me4C4BPh) (1d; Fe-B = 215.1(4) pm, Fe-H = 147(3) pm, B-H = 151(3) pm) and (C5H4Me)FeH(2,5-Me2C4H2-BPh) (1f; Fe-B = 215.5(2) pm, Fe-H = 147.5(23) pm, B-H = 146.1(26) pm) as determined by low-temperature X-ray diffraction show the presence of an Fe-H-B three-center bond with a weak B-H interaction. In solution 1a establishes a mobile equilibrium between the ground state 1a-G with Fe-H-B three-center bonding and the agostic isomer 1a-A with Fe-H-C-2(C4H4B) three-center bonding with an estimated DELTAG = 1.4 kcal/mol. The hydridic proton and the 2-/5-protons of the borole ring undergo fast intramolecular exchange (T(c) = 333 K at 80 MHz and DELTAG(double dagger)333 = 17.0 +/- 0.7 kcal/mol for 1a). A merry-go-round of the three H atoms involved with one hydrogen crossing the exo face of the borole ligand is proposed as an exchange mechanism. The bonding in CpFeH(C4H4BH) is analyzed by means of extended Huckel calculations, which confirm the Fe-H-B three-center bonding. Exploratory extended Huckel calculations also support the existence of agostic isomers as well as the proposed exchange mechanism. Cyclic voltammetry revealed the existence of the 17e complex CpFe(C4H4BPh) (5a), which is characterized by its EPR and paramagnetic H-1 NMR spectra. 1a reacts with CNBu(t) to give the boracyclopentenyl complex CpFe(CNBu(t)) (C4H5BPh) (9a) and, probably via the intermediate Fe(CNBu(t))(C4H4BPh) (C5H6) (10), the borole complex Fe(CNBu(t))3(C4H4BPh) (11a) and 1 equiv of cyclopentadiene. Labeling experiments show that the shift of the hydridic hydrogen to the borole and Cp ligands, respectively, is an intramolecular process. 1c reacts analogously.

  (Original English) (Borole)tricarbonyliron complexes Fe(CO)3(3,4-R1(2)C4H2BPh) (3a, R1 = H; 3b, R1 = Me) react with cyclopentadiene under irradiation to give the hydrides CpFeH(3,4-R1(2)C4H2BPh) (1a,b). Deprotonation by NaH in THF produces the borataferrocene anions [CpFe(3,4-R1(2)C4H2BPh)]-(5a-, 5b-). These can be alkylated in the 2-/5-position by alkyl iodides in the presence of NaH to give 2,5-dialkyl hydride derivatives: e.g. CpFeH(2,5-R2(2)C4H2BPh) (1c, R2 = Me; 1g, R2 = CH2=CH( )4; 1h, R2 = ( )2CH ). The structures of CpFeH(2,3,4,5-Me4C4BPh) (1d; Fe-B = 215.1(4) pm, Fe-H = 147(3) pm, B-H = 151(3) pm) and (C5H4Me)FeH(2,5-Me2C4H2-BPh) (1f; Fe-B = 215.5(2) pm, Fe-H = 147.5(23) pm, B-H = 146.1(26) pm) as determined by low-temperature X-ray diffraction show the presence of an Fe-H-B three-center bond with a weak B-H interaction. In solution 1a establishes a mobile equilibrium between the ground state 1a-G with Fe-H-B three-center bonding and the agostic isomer 1a-A with Fe-H-C-2(C4H4B) three-center bonding with an estimated ΔG = 1.4 kcal/mol. The hydridic proton and the 2-/5-protons of the borole ring undergo fast intramolecular exchange (T(c) = 333 K at 80 MHz and Δ‡G(333) = 17.0 ± 0.7 kcal/mol for 1a). A merry-go-round of the three H atoms involved with one hydrogen crossing the exo face of the borole ligand is proposed as an exchange mechanism. The bonding in CpFeH( H) is analyzed by means of extended Huckel calculations, which confirm the Fe-H-B three-center bonding. Exploratory extended Huckel calculations also support the existence of agostic isomers as well as the proposed exchange mechanism. Cyclic voltammetry revealed the existence of the 17e complex CpFe( Ph) (5a), which is characterized by its EPR and paramagnetic H-1 NMR spectra. 1a reacts with CNBu(t) to give the boracyclopentenyl complex CpFe(CNBu(t)) (C4H5BPh) (9a) and, probably via the intermediate Fe(CNBu(t))( Ph) (C5H6) (10), the borole complex Fe(CNBu(t))3( Ph) (11a) and 1 equiv of cyclopentadiene. Labeling experiments show that the shift of the hydridic hydrogen to the borole and Cp ligands, respectively, is an intramolecular process. 1c reacts analogously. (Translated Chinese) 含有硼杂环戊二烯配位的三羰基铁配合物 Fe(CO)3(3,4-R1(2)C4H2BPh)（3a，R1 = H；3b，R1 = Me）在光照条件下与环戊二烯反应生成氢化物 CpFeH(3,4-R1(2)C4H2BPh)（1a,b）。在四氢呋喃中使用氢化钠去质子化，生成硼杂铁磁烯阴离子 [CpFe(3,4-R1(2)C4H2BPh)]-（5a-, 5b-）。这些阴离子在氢化钠存在下可与烷基碘化物反应，在2/5位上进行烷基化，生成双烷基氢化物衍生物：例如 CpFeH(2,5-R2(2)C4H2BPh)（1c，R2 = Me；1g，R2 = =CH( )4；1h，R2 = ( )2CH ）。通过低温X射线衍射确定的CpFeH(2,3,4,5-Me4C4BPh)（1d；Fe-B = 215.1(4) pm，Fe-H = 147(3) pm，B-H = 151(3) pm）和 (C5H4Me)FeH(2,5-Me2C4H2-BPh)（1f；Fe-B = 215.5(2) pm，Fe-H = 147.5(23) pm，B-H = 146.1(26) pm）的结构显示存在一个Fe-H-B三中心键，并伴有较弱的B-H相互作用（[Fe-H = 147.5(23) pm]）。在溶液中，1a处于基态1a-G（Fe-H-B三中心键）与奥古斯特异构体1a-A（Fe-H-C-2( )三中心键）之间的动态平衡，估计ΔG = 1.4 kcal/mol。氢化物质子和硼杂环戊二烯环上的2/5位质子发生快速的分子内交换（T(c) = 333 K，80 MHz下Δ‡G(333) = 17.0 ± 0.7 kcal/mol）。提出了一种“旋转木马”式的氢原子交换机制，其中三个氢原子参与交换，其中一个氢原子穿过硼杂配体的外侧面。通过扩展Hückel计算分析CpFeH( H)中的键合关系，证实了Fe-H-B三中心键的存在。初步的扩展Hückel计算还支持奥古斯特异构体的存在以及所提出的交换机制。循环伏安法揭示了17e复合物CpFe( Ph)（5a）的存在，其特性通过电子顺磁共振（EPR）和顺磁性H-1 NMR光谱得到表征。1a与CNBu(t)反应生成硼环戊烯基配合物CpFe(CNBu(t))(C4H5BPh)（9a），并通过中间体Fe(CNBu(t))( Ph)( )（10），进一步生成硼杂环配合物Fe(CNBu(t))3( Ph)（11a），并释放1当量的环戊二烯。标记实验表明，氢化物的氢转移到硼杂环和Cp配体的过程是一个分子内过程。1c的反应行为与1a类似。 (End of Translation)
• Herberich, Gerhard E.; Carstensen, Tobias; Englert, Ulli, Chemische Berichte, 1992, vol. 125, # 11, p. 2351 - 2358
  作者：Herberich, Gerhard E.、Carstensen, Tobias、Englert, Ulli

  DOI：——

  日期：——