Borirene

Borirene
Names
Other names
1H-Boriren-1-yl
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C2H3B/c1-2-3-1/h1-3H
    Key: UVBXRPNQDJLHAH-UHFFFAOYSA-N
  • 1H-Boriren-1-yl: InChI=1S/C2H2B/c1-2-3-1/h1-2H
    Key: OIJTZPGWOYZZSN-UHFFFAOYSA-N
  • B1C=C1
  • 1H-Boriren-1-yl: [B]1C=C1
Properties
C2H3B
Molar mass 37.86 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Borirenes are a unique class of three-membered heterocyclic compounds characterized by an unsaturated boron atom within their ring structure. First computationally predicted by John Pople and Paul von Rague Schleyer in 1981,[1] the simplest borirene, (CH)2BH, is isoelectronic with the cyclopropenium cation and exhibits Hückel aromaticity.[2] Borirenes undergo ring-opening reactions with polar reagents[3][4][5] and form Lewis adducts,[6][7][8] due to the significant ring strain in its three-membered structure and the presence of an empty p orbital on the boron atom. The balance of these two properties leads to unique properties as a ligand for transition metals, in addition to observation of photochemical rearrangement and ring expansion. While borirenes were first discovered in the 1980s, new derivatives such as benzoborirenes have led to renewed interest in the field, with their potential applications yet to be fully explored.

Figure 1. The first reported X-ray crystal structure of trimesitylboracyclopropene,[5] an example of a class of compounds known as borirenes.


Electronic Structure

Both the σ- and π- framework of borirenes contribute significantly to its diverse reactivity. It is best shown by comparing borirenes to the isoelectronic cyclopropenyl cation:[9]

Figure 2. Representation of molecular orbitals and their relative energies of the σ-, π- framework in cyclopropenyl cation. Only the four most relevant MOs of the σ-framework are shown above.

Although 2π Hückel aromaticity stabilizes the π-framework, three-membered ring systems like cyclopropane experience significant ring strain with bond angles of approximately 60°, deviating significantly from the 120° angles typical of sp2-hybridized carbons. This strain limits 2s-2p orbital mixing, and the σ-framework have significant π-character in terms of reactivity.[10] This leads to the energies of both frameworks being relatively close in energy, leading to interesting interactions overall. From the isolobal principle, we can expect the bonding properties to be similar in borirenes:  

Figure 3. Computed molecular orbital energies of borirene (C2H3B). The molecular orbitals are ordered from lowest energy (left) to highest energy (right). Computed with B3YLP-D3BJ/def2-TZVP level of theory in Orca 6.0.1.

Seven molecular orbitals are depicted in Figure 3. For the simplest borirene, C2H3B, the two highest occupied molecular orbitals (HOMOs) are from the σ-framework, while the two lowest unoccupied molecular orbitals (LUMO) are from the π-framework. Substituting one carbon atom with boron, due to its lower electronegativity, disrupts degeneracy. With σ- and π- orbitals close in energy, the HOMO−1 and HOMO (from the σ-framework) can act as a π-donor and σ-donor, respectively, while the LUMO and LUMO+1 serve as both σ-acceptors and π-acceptors. A detailed computational study on borirenes by Paul von Ragué Schleyer and coworkers have predicted these molecules to undergo facile dimerization into 1,4-diboracyclohexadiene.[11]

The orbital energetics are highly tunable via substituent effects: electron-withdrawing groups lower the HOMO energy, whereas electron-donating groups raise the LUMO energy, as shown in Figure 4.[9] Characterized borirenes to date are stabilized predominantly by electron-rich, strong σ- and π-donor substituents that raise the LUMO and lowers the HOMO energy. Due to their inherent reactivity, sterically demanding groups such as m-terphenyl or mesityl substituents are commonly employed to enhance kinetic stability.

Figure 4. Relative effects of electron-withdrawing groups (EWG) and electron-donating groups (EDG) to a simple alkene. Both EWG and EDG have very similar effects to the σ-framework and π-framework in borirenes.

Synthesis

The simplest borirene, (CH)2BH, which was prepared via a reaction between an atomic boron atom and ethylene, was first identified using matrix isolation spectroscopy by Lanzisera et al. in 1997, and later confirmed with the crossed molecular beam method by Balucani et al.[12][13] Substituted borirenes are typically prepared starting from an alkyne, and are prepared through either a rearrangement or a borylene pathway as shown in Scheme 1:

Scheme 1. Currently reported methods in the literature to prepare borylenes. The borylene pathway is accessible by either generating a in situ borylene intermediate or transferring a terminal borylene ligand from an electron-rich metal complex. The rearrangement pathway is accessible by photoinduced rearrangement of an alkynyl-borane or formation of an alkynyl-diborane intermediate. The proposed mechanism shown below are examples of potential mechanisms for the reaction, with the possibility of alternative mechanisms. (Ph = phenyl, tBu = tert-butyl, Dipp = 1,3-diisopropylphenyl, Mes = 1,3,5-trimethylphenyl)

Borylene addition is a widely utilized method for the synthesis of simple borirenes. The first identification of a substituted borirene was reported by Van Der Kerk et al., achieved through GC-MS analysis of a one-pot reaction involving MeBBr2, KC8, and di-tert-butylacetylene under reflux conditions.[14] The proposed mechanism suggests the formation of a highly reactive methylborylene intermediate, formed via the elimination of two equivalents of potassium bromide. This intermediate subsequently undergoes a [2+1] cycloaddition with the alkyne precursor, leading to the formation of the borirene framework. Similarly, a photochemical approach utilizing tris(triphenylsilyl)borane as a precursor has been reported, wherein a highly reactive silylborylene intermediate reacts with bis(trimethylsilyl)acetylene to form analogous products.[15] This synthetic pathway is limited by the stability of the starting materials when exposed to strong reducing agents, the inherent instability of the borylene intermediate, and low yields.

An alternative and milder route to prepare borirenes involve the use of terminal borylene complexes, which are able to efficiently transfer the borylene moiety to alkynes under photolytic conditions. Electron-rich complexes such as [(OC)5Cr=BX] have emerged as key reagents in this context and have been extensively studied by Braunschweig and co-workers.[6][16][17][18][19][20][21][22]

Borirenes can also be synthesized by rearranging internal alkynes bonded directly to boron substituents. For instance, alkyl-substituted diboranes react with trimethylstannylalkynes to form alkynyl-diborane intermediates, which quickly rearrange into borirene products. Alternatively, photoinduced rearrangement of alkynyl-boranes provides another efficient pathway for borirene synthesis.[5][23]

Reactivity

Scheme 2. General reactivity of borirenes currently described in the literature. (Mes = 1,3,5-trimethylphenyl)

Similar to other tricoordinate boron compounds, borirenes readily form Lewis adducts.[6][7][8] Strong Lewis bases like N-heterocyclic carbenes (NHCs) bind efficiently to borirenes but can be displaced by introducing stronger Lewis acids, such as tris(pentafluorophenyl)borane.[6] Pyridine has also been shown to bind reversibly to borirenes, illustrating the milder Lewis acidity of borirenes due to the aromatic π-framework.[6] In cases where the boron atom is directly bonded to a metal fragment capable of functioning as a leaving group—such as FeCp*(CO)2—two equivalents of NHCs can displace the metal fragment, resulting in a formally positively charged tetracoordinate boron center, with [FeCp*(CO)2]− acting as the counteranion.[7]


Similar to other highly strained cyclic molecules like cyclopropanes, the significant π-character of the σ−framework enables borirenes to undergo ring-opening reactions.[3][4][5] Polar reagents, such as hydrogen chloride (HCl) and alcohols (HOR), readily cleave the B–C bond, with the more electropositive component bonding to carbon. With the frontier orbitals of borirenes being characterized by a HOMO dominated by the σ-framework and a LUMO dominated by the π-framework, this facilitates not only ring-opening reactions and Lewis adduct formation but also other transformations, such as photoinduced rearrangements and coordination as ligands to transition metals. As shown in Scheme 2, when an electron-rich metal fragment is bonded to one of the carbon atoms of the borirene, photoinduced rearrangement can occur to yield alkynyl-boranes.[4][22] Despite their inherent reactivity, substituted borirenes exhibit remarkable thermal stability, tolerating temperatures up to 200 °C. However, they slowly decompose in oxygen, regenerating the original alkyne starting material and yielding trace amounts of a five-membered ring-expansion product, dioxaborole, as detected by GC-MS.[5]

Potential Ligand Properties

Scheme 3. Preparation of the platinum complex with supported B-C σ coordination.[24] (Mes = 1,3,5-trimethylphenyl, Ph = phenyl)

Borirenes exhibit promising potential as ligands. For example, introducing an electron-rich metal complex, such as tetrakis(triethylphosphine)platinum(0), to a borylene complex induces B–C σ-bond coordination instead of cleavage.[24] This is shown in Scheme 3. The platinum fragment benefits from strong σ- and π-donation from the σ-framework and moderate π-acceptance from the π-framework. Notably, no dπ−σ*B-C interaction is observed, indicating that B−C bond activation is unfavorable.

Scheme 4. Borylene transfer to diphenylacetylene using a chromium carbonyl complex with a terminal borylene ligand. Free borirene and η3-bound borirene was reported to form in a 4:1 ratio. The authors also noted that the η3-bound borirene could not be made with addition of [Cr(CO)3(CNEt)3]. The X-ray crystal structure of the η3-bound borirene was also reported.[17]

Braunschweig and coworkers further demonstrated the potential of borirenes as ligands. Reacting diphenylacetylene with a terminal borylene complex, as shown in Scheme 4, produced both a free borirene and an η3-bound chromium-borirene complex in a 4:1 ratio.[17] The authors proposed that the η3-bound chromium-borirene complex acts as an intermediate in the borylene-transfer process.

Computational investigations further highlight the distinct electronic properties of borirene ligands. Comparing the model complex (1,3,5-triisopropylbenzene)Cr(CO)3 with the minor product, energy decomposition analysis (EDA) revealed a ~1.6-fold increase in key parameters—attractive electrostatic interactions, orbital interactions, and repulsive Pauli interactions— indicating that borirene is a stronger ligand than CO.

Benzoborirenes

Scheme 5. Synthesis and reactivity of characterized benzoborirene compounds. (NHC = N-heterocyclic compound, Mes* = 1,3,5-tri-tert-butylphenyl, Ar = aromatic ring)

Benzoborirenes represent a novel and highly reactive class of borirene derivatives, where the borirene ring is fused to a benzene ring via a shared C=C bond.[2] DFT calculations suggest that the local aromaticity of the borirene unit in benzoborirene is comparable to that of the parent borirene. However, this fusion introduces significant ring strain due to structural deformation of the benzene ring in an anti-Mills-Nixon fashion, resulting in shorter C=C bonds in the fused atoms. This strain also enhances the inherent Lewis acidity of the boron center.[2][25]

The fleeting benzoborirene was first detected experimentally as an intermediate by Bettinger and coworkers in 2002.[26] In 2018, the Bettinger group characterized the first stable benzoborirene compound using NMR spectroscopy, identifying an NHC-stabilized benzoborirene that rapidly dimerizes to form an NHC-stabilized 9,10-diboraanthracene. Notably, dimerization can be avoided by stabilizing the boron center with bulky, electron-rich groups.[27]

In 2020, the Ye group advanced the field by synthesizing a benzoborirene stabilized with bis(trimethylsilyl)amine (HMDS) using Cp2ZrPh2 and HMDSBBr2 as key reagents. Their foundings revealed that benzoborirenes exhibit distinct reactivity compared to borirenes. Strong donors, such as isonitriles and N-heterocyclic carbenes, induced ring-expansion and ring-opening reactions, respectively, diverging from the typical Lewis adduct formation observed for borirenes.[28][29]

In 2022, the Bettinger group synthesized a m-terphenyl-stabilized benzoborirene and conducted detailed reactivity studies. Consistent with their heightened reactivity, benzoborirenes were found to form Lewis adducts only with weak ligands such as pyridine. Methanol, as observed with borirenes, induced ring-opening reactions. More complex transformations were observed with phosphine oxides, aldehydes, and isonitriles, which triggered ring-expansion reactions, leading to the formation of five-membered boron heterocyclic species.[30] Two years later in 2024, the Bettinger group expanded on the reactivity of benzoborienes by showing its potential to undergo formal (2+2) ring expansions, as shown in Scheme 6.[31] This contrasts the reactivity shown by cyclopropa[b]naphthalene, which can be considered an all-carbon analogue of the benzoborirene, which are known to undergo formal [4+2] and [4+2] cycloaddition reactions with highly reactive dienophiles, such as 4,-phenyl-1,2,4-triazoline-3,5-dione (PTAD) and 3,6-di-(4-pyridyl)-1,2,4,5-tetrazine (4,4’-bptz).[32][33]

Scheme 6. Formal (2+2) ring expansions with strong nitrogen-based dienophiles and benzoborirenes, conducted by Bettinger and coworkers. (Tripp = 1,3,5-triisopropylphenyl)

References

  1. ^ Krogh-Jespersen, K.; Cremer, D.; Dill, J. D.; Pople, J. A.; Schleyer, P. R. (1981-05-01). "Aromaticity in small rings containing boron and carbon, ((CH)2(BH)n, n = 1,2): comarisons with isoelectronic carbocations. The decisive roles of orbital mixing and nonbonded 1,3-interactions in the structures of four-membered rings". Journal of the American Chemical Society. 103 (10): 2589–2594. Bibcode:1981JAChS.103.2589K. doi:10.1021/ja00400a018. ISSN 0002-7863.
  2. ^ a b c Wang, Junyi; Ye, Qing (2024-02-21). "Borirenes and Boriranes: Development and Perspectives". Chemistry – A European Journal. 30 (11): e202303695. doi:10.1002/chem.202303695. ISSN 0947-6539. PMID 38085103.
  3. ^ a b Braunschweig, Holger; Herbst, Thomas; Radacki, Krzysztof; Frenking, Gernot; Celik, Mehmet Ali (2009-11-09). "Chemoselective Boron–Carbon Bond Cleavage by Hydroboration of Borirenes". Chemistry – A European Journal. 15 (44): 12099–12106. doi:10.1002/chem.200901749. ISSN 0947-6539. PMID 19780118.
  4. ^ a b c Braunschweig, Holger; Ye, Qing; Radacki, Krzystof; Kupfer, Thomas (2011). "Reactivity of a platinum-substituted borirene". Dalton Transactions. 40 (14): 3666–3670. doi:10.1039/c0dt01694b. ISSN 1477-9226. PMID 21331418.
  5. ^ a b c d e Eisch, John J.; Shafii, Babak; Odom, Jerome D.; Rheingold, Arnold L. (1990-02-01). "Bora-aromatic systems. Part 10. Aromatic stabilization of the triarylborirene ring system by tricoordinate boron and facile ring-opening with tetracoordinate boron". Journal of the American Chemical Society. 112 (5): 1847–1853. Bibcode:1990JAChS.112.1847E. doi:10.1021/ja00161a031. ISSN 0002-7863.
  6. ^ a b c d e Braunschweig, Holger; Damme, Alexander; Dewhurst, Rian D.; Ghosh, Sundargopal; Kramer, Thomas; Pfaffinger, Bernd; Radacki, Krzysztof; Vargas, Alfredo (2013-02-06). "Electronic and Structural Effects of Stepwise Borylation and Quaternization on Borirene Aromaticity". Journal of the American Chemical Society. 135 (5): 1903–1911. Bibcode:2013JAChS.135.1903B. doi:10.1021/ja3110126. ISSN 0002-7863. PMID 23305227.
  7. ^ a b c Braunschweig, Holger; Dewhurst, Rian D.; Ferkinghoff, Katharina (2016). "Carbene-induced synthesis of the first borironium cations using the [(η 5 -C 5 Me 5 )Fe(CO) 2 ] − anion as an unlikely leaving group". Chemical Communications. 52 (1): 183–185. doi:10.1039/C5CC07503C. ISSN 1359-7345. PMID 26511336.
  8. ^ a b Pues, Christine; Berndt, Armin (1984-04-01). "1- tert -Butylborirenes". Angewandte Chemie International Edition in English. 23 (4): 313–314. doi:10.1002/anie.198403131. ISSN 0570-0833.
  9. ^ a b Fleming, Ian (2010-02-26). Molecular Orbitals and Organic Chemical Reactions (1 ed.). Wiley. doi:10.1002/9780470689493. ISBN 978-0-470-74658-5.
  10. ^ Dewar, Michael J. S. (1984-02-01). "Chemical implications of .sigma. conjugation". Journal of the American Chemical Society. 106 (3): 669–682. Bibcode:1984JAChS.106..669D. doi:10.1021/ja00315a036. ISSN 0002-7863.
  11. ^ Budzelaar, Peter H. M.; Van der Kerk, Sies M.; Krogh-Jespersen, Karsten.; Schleyer, Paul v. R. (1986-07-01). "Dimerization of borirene to 1,4-diboracyclohexadiene. Structures and stabilities of (CH)4(BH)2 molecules". Journal of the American Chemical Society. 108 (14): 3960–3967. Bibcode:1986JAChS.108.3960B. doi:10.1021/ja00274a017. ISSN 0002-7863.
  12. ^ Lanzisera, Dominick V.; Hassanzadeh, Parviz; Hannachi, Yacine; Andrews, Lester (1997-12-17). "Identification of the Borirene Molecule, (CH) 2 BH: Matrix Isolation FTIR and DFT Calculations for Five Vibrational Modes of Six Isotopic Molecules". Journal of the American Chemical Society. 119 (50): 12402–12403. Bibcode:1997JAChS.11912402L. doi:10.1021/ja973094u. ISSN 0002-7863.
  13. ^ Balucani, Nadia; Asvany, Oskar; Lee, Yuan T.; Kaiser, Ralf I.; Galland, Nicolas; Hannachi, Yacine (2000-11-01). "Observation of Borirene from Crossed Beam Reaction of Boron Atoms with Ethylene". Journal of the American Chemical Society. 122 (45): 11234–11235. Bibcode:2000JAChS.12211234B. doi:10.1021/ja001447a. ISSN 0002-7863.
  14. ^ van der Kerk, Sies M.; Budzelaar, Peter H. M.; van der Kerk-van Hoof, Anca; van der Kerk, Gerrit J. M.; von Ragué Schleyer, Paul (1983-01-01). "Synthesis of Borirenes and Diboretenes — a Novel Class of 2π-Aromatic Compounds". Angewandte Chemie International Edition in English. 22 (1): 48. doi:10.1002/anie.198300481. ISSN 0570-0833.
  15. ^ Pachaly, Bernd; West, Robert (1984-06-01). "Photochemical Generation of Triphenylsilylboranediyl (C 6 H 5 ) 3 SiB: from Organosilylboranes". Angewandte Chemie International Edition in English. 23 (6): 454–455. doi:10.1002/anie.198404541. ISSN 0570-0833.
  16. ^ Braunschweig, Holger; Damme, Alexander; Dewhurst, Rian D.; Kelch, Hauke; Macha, Bret B.; Radacki, Krzysztof; Vargas, Alfredo; Ye, Qing (2015-02-02). "Platinum trans -Bis(borirene) Complexes Displaying Coplanarity and Communication Across a Platinum Metal Center". Chemistry – A European Journal. 21 (6): 2377–2386. doi:10.1002/chem.201405803. ISSN 0947-6539. PMID 25430871.
  17. ^ a b c Braunschweig, Holger; Dewhurst, Rian D.; Radacki, Krzysztof; Tate, Christopher W.; Vargas, Alfredo (2014-06-10). "Trihapto Ligation of a Borirene to a Single Metal Atom: A Heterocyclic Analogue of the η 3 -Cyclopropenyl Ligand". Angewandte Chemie International Edition. 53 (24): 6263–6266. doi:10.1002/anie.201402815. ISSN 1433-7851. PMID 24802284.
  18. ^ Braunschweig, Holger; Fernández, Israel; Frenking, Gernot; Radacki, Krzysztof; Seeler, Fabian (2007-07-02). "Synthesis and Electronic Structure of a Ferroborirene". Angewandte Chemie International Edition. 46 (27): 5215–5218. doi:10.1002/anie.200700382. ISSN 1433-7851. PMID 17538918.
  19. ^ Braunschweig, Holger; Herbst, Thomas; Rais, Daniela; Ghosh, Sundargopal; Kupfer, Thomas; Radacki, Krzysztof; Crawford, Andrew G.; Ward, Richard M.; Marder, Todd B.; Fernández, Israel; Frenking, Gernot (2009-07-01). "Borylene-Based Direct Functionalization of Organic Substrates: Synthesis, Characterization, and Photophysical Properties of Novel π-Conjugated Borirenes". Journal of the American Chemical Society. 131 (25): 8989–8999. Bibcode:2009JAChS.131.8989B. doi:10.1021/ja902198z. ISSN 0002-7863. PMID 19480461.
  20. ^ Braunschweig, Holger; Herbst, Thomas; Rais, Daniela; Seeler, Fabian (2005-11-18). "Synthesis of Borirenes by Photochemical Borylene Transfer from [(OC) 5 MBN(SiMe 3 ) 2 ] (M=Cr, Mo) to Alkynes". Angewandte Chemie International Edition. 44 (45): 7461–7463. doi:10.1002/anie.200502524. ISSN 1433-7851. PMID 16231387.
  21. ^ Braunschweig, Holger; Ye, Qing; Radacki, Krzystof (2009). "Borylene-based functionalization of Pt–alkynyl complexes by photochemical borylene transfer from [(OC)5CrBN(SiMe3)2]". Chemical Communications (45): 6979–6981. doi:10.1039/b915926f. ISSN 1359-7345. PMID 19904367.
  22. ^ a b Braunschweig, Holger; Ye, Qing; Radacki, Krzysztof; Brenner, Peter; Frenking, Gernot; De, Susmita (2011-01-03). "Borylene-Based Functionalization of Iron-Alkynyl-σ-Complexes and Stepwise Reversible Metal-Boryl-to-Borirene Transformation: Synthesis, Characterization, and Density Functional Theory Studies". Inorganic Chemistry. 50 (1): 62–71. doi:10.1021/ic1010874. ISSN 0020-1669. PMID 20712372.
  23. ^ Eisch, John J.; Shafii, Babak; Rheingold, Arnold L. (1987-04-01). "Bora-aromatic systems. 9. Di-.pi.-methane-like photorearrangement of dimesityl(mesitylethynyl)borane: synthesis, structure, and aromaticity of trimesitylborirene". Journal of the American Chemical Society. 109 (8): 2526–2528. Bibcode:1987JAChS.109.2526E. doi:10.1021/ja00242a055. ISSN 0002-7863.
  24. ^ a b Braunschweig, Holger; Brenner, Peter; Dewhurst, Rian D.; Krummenacher, Ivo; Pfaffinger, Bernd; Vargas, Alfredo (2012-05-29). "Unsupported boron–carbon σ-coordination to platinum as an isolable snapshot of σ-bond activation". Nature Communications. 3 (1): 872. Bibcode:2012NatCo...3..872B. doi:10.1038/ncomms1884. ISSN 2041-1723. PMID 22643899.
  25. ^ Hahn, Jennifer; Keck, Constanze; Maichle-Mössmer, Cäcilia; von Grotthuss, Esther; Ruth, Paul Niklas; Paesch, Alexander; Stalke, Dietmar; Bettinger, Holger F. (2018-12-12). "Synthesis and Ring Strain of a Benzoborirene- N -Heterocyclic Carbene Adduct". Chemistry – A European Journal. 24 (70): 18634–18637. doi:10.1002/chem.201804629. ISSN 0947-6539. PMID 30444011.
  26. ^ Kaiser, Ralf I.; Bettinger, Holger F. (2002). "Gas-Phase Detection of the Elusive Benzoborirene Molecule". Angewandte Chemie International Edition. 41 (13): 2350–2352. doi:10.1002/1521-3773(20020703)41:13<2350::AID-ANIE2350>3.0.CO;2-T. ISSN 1521-3773. PMID 12203589.
  27. ^ Hahn, Jennifer; Keck, Constanze; Maichle-Mössmer, Cäcilia; von Grotthuss, Esther; Ruth, Paul Niklas; Paesch, Alexander; Stalke, Dietmar; Bettinger, Holger F. (2018-12-12). "Synthesis and Ring Strain of a Benzoborirene- N -Heterocyclic Carbene Adduct". Chemistry – A European Journal. 24 (70): 18634–18637. doi:10.1002/chem.201804629. ISSN 0947-6539. PMID 30444011.
  28. ^ Zhang, Hui; Wang, Junyi; Yang, Weiguang; Xiang, Libo; Sun, Weicheng; Ming, Wenbo; Li, Yinxin; Lin, Zhenyang; Ye, Qing (2020-10-14). "Solution-Phase Synthesis of a Base-Free Benzoborirene and a Three-Dimensional Inorganic Analogue". Journal of the American Chemical Society. 142 (41): 17243–17249. Bibcode:2020JAChS.14217243Z. doi:10.1021/jacs.0c06538. ISSN 0002-7863. PMID 32941023.
  29. ^ Liu, Xiaocui; Heinz, Myron; Wang, Junyi; Tan, Leibo; Holthausen, Max C.; Ye, Qing (2023-12-18). "A Journey from Benzoborirene to Benzoborole-Supported 1,2-Diimine and Antiaromatic Borolediide". Angewandte Chemie International Edition. 62 (51): e202312608. doi:10.1002/anie.202312608. ISSN 1433-7851. PMID 37758684.
  30. ^ Sindlinger, Marvin; Ströbele, Markus; Maichle-Mössmer, Cäcilia; Bettinger, Holger F. (2022). "Kinetic stabilization allows structural analysis of a benzoborirene". Chemical Communications. 58 (17): 2818–2821. doi:10.1039/D1CC06588B. ISSN 1359-7345. PMID 35050291.
  31. ^ Sindlinger, Marvin; Biebl, Sonja; Ströbele, Markus; Bettinger, Holger F. (2024). "Formal (2+2) ring expansion prevails over (4+2) cycloaddition of a kinetically stabilized benzoborirene with reactive cycloaddends". Chemical Communications. 60 (73): 9986–9989. doi:10.1039/D4CC02888K. ISSN 1359-7345. PMID 39175434.
  32. ^ Halton, B; Russell, Sgg (1990). "Studies in the Cycloproparene Series: Cycloaddition Reactions With 1,3-Diphenylisobenzofuran". Australian Journal of Chemistry. 43 (12): 2099. doi:10.1071/CH9902099. ISSN 0004-9425.
  33. ^ Neidlein, Richard; Tadesse, Lema (1988-02-03). "Synthese von Dimethyl-4a,8a-methanophthalazin-1,4-dicarboxylat und Derivaten". Helvetica Chimica Acta. 71 (1): 249–253. doi:10.1002/hlca.19880710127. ISSN 0018-019X.