Synthesis and Reactions of Borazines

Abstract

Given the wide array of current applications of borazine-based materials, synthetic access to these compounds is of importance. This review summarizes the many ways of preparing borazines and its carbo-substituted analogues. In addition, the functionalization of borazines is covered. The synthesis of molecules incorporating more than one borazine units as well as aspects of unsymmetrically substituted borazines are not included. The literature has been covered comprehensively until the end of 2020.

1 Introduction: Structure and Properties of Borazine

2 Synthesis of Parent Borazine

3 Synthesis of N-Substituted Borazines

4 Synthesis of B-Halo/B-Halo-N-Substituted Borazines

5 Synthesis of B-Substituted Borazines

6 Synthesis of Polycyclic Borazines Containing One Borazine Ring

7 Modifications or Hydrolysis of the Borazine Ring

8 Borazine Metal Complexes

9 Outlook and Conclusion

Key words

borazine - aromaticity - synthesis - supramolecular chemistry - boron - nitrogen

Publication History

Received: 04 July 2021

Accepted after revision: 02 November 2021

Accepted Manuscript online:
02 November 2021

Article published online:
24 February 2022

• References

• 1 Bonifazi D, Fasano F, Lorenzo-Garcia MM, Marinelli D, Oubaha H, Tasseroul J. Chem. Commun. 2015; 51: 15222
• 2 Mellon EK, Lagowski JJ. The Borazines . In Advances in Inorganic Chemistry and Radiochemistry, Vol. 5. Emeléus HJ, Sharpe AG. Academic Press; New York: 1963: 259-305
• 3 Stock A, Pohland E. Chem. Ber. 1926; 59: 2210
• 4 Rideal S. Chem. Ber. 1889; 22: 992
• 5a Stock A, Wierl R. Z. Anorg. Allg. Chem. 1931; 203: 228
• 5b Bauer SH. J. Am. Chem. Soc. 1938; 60: 524
• 5c Harshbarger W, Lee GH, Porter RF, Bauer SH. Inorg. Chem. 1969; 8: 1683

For the X-ray crystallographic determination, see:
• 5d Boese R, Maulitz AH, Stellberg P. Chem. Ber. 1994; 127: 1887
• 6 Niedenzu K, Dawson JW. Chemistry of Boron-Nitrogen Compounds . In Chemistry of Boron and Its Compounds . Muetterties EL. Wiley; New York: 1967: 377-442
• 7 Hohnstedt LF, Schaeffer GW. Borazine Chemistry . In Advances in Chemistry, Vol. 32, Chap. 26. American Chemical Society; Washington DC: 1961: 232-240
• 8 Fink WH, Richards JC. J. Am. Chem. Soc. 1991; 113: 3393
• 9 Islas R, Chamorro E, Robles J, Heine T, Santos JC, Merino G. Struct. Chem. 2007; 18: 833
• 10 Benker D, Klapötke TM, Kuhn G, Li J, Miller C. Heteroat. Chem. 2005; 16: 311
• 11 Schleyer P. vR, Jiao H. Pure Appl. Chem. 1996; 68: 209
• 12 Kiran B, Phukan AK, Jemmis ED. Inorg. Chem. 2001; 40: 3615
• 13 Dennis GR, Ritchie GL. D. J. Phys. Chem. 1993; 97: 8403
• 14 Shen W, Li M, Li Y, Wang S. Inorg. Chim. Acta 2007; 360: 619
• 15 Baranac-Stojanović M. J. Phys. Chem. A 2013; 117: 11540
• 16 Newsom HC, English WD, McCloskey AL, Woods WG. J. Am. Chem. Soc. 1961; 83: 4134
• 17 Pino-Rios R, Vásquez-Espinal A, Yañez O, Tiznado W. RSC Adv. 2020; 10: 29705
• 18 Niedenzu K, Dawson JW. Boron-Nitrogen Compounds. In Anorganische und Allgemeine Chemie in Einzeldarstellungen, Vol. 6. Springer; Berlin: 1965: 85-126
• 19 Eddy LB, Smith SH, Miller RR. J. Am. Chem. Soc. 1955; 77: 2105
• 20 Beyer H, Jenne H, Hynes JB, Niedenzu K. Chemistry of B-Fluorinated Borazines . In Advances in Chemistry, Vol. 42, Chap. 26. American Chemical Society; Washington DC: 1964: 266-272
• 21a Crawford BL. Jr, Edsall JT. J. Chem. Phys. 1939; 7: 223
• 21b Price WC, Fraser RD. B, Robinson TS, Longuet-Higgins HC. Faraday Discuss. 1950; 9: 131
• 22 Davis BL, Rekken BD, Michalczyk R, Garner 3rd. EB, Dixon DA, Kalviri H, Baker RT, Thorn DL. Chem. Commun. 2013; 49: 9095
• 23a Platt JR, Klevens HB, Schaeffer GW. J. Chem. Phys. 1947; 15: 598
• 23b Jacobs LE, Platt JR, Schaeffer GW. J. Chem. Phys. 1948; 16: 116
• 24 Robinson B, Shepherd DM, Woodhead JL, Fletcher JM, Corbett WM, McKay JE, Taylor W, Banks BE. C, Kertes AS, Beck A, Clark J, Lister JH, Smith TD, Hinton IG, Webb RF, Coates GE, Livingstone JG, Cremlyn RJ. W, Casy AF, Coutts RT, Hooper M, Wibberley DG, Champion NG. S, Foster R, Mackie RK. J. Chem. Soc. 1961; 5037
• 25 Chiavarino B, Crestoni ME, Fornarini S. J. Am. Chem. Soc. 1999; 121: 2619
• 26 Kervyn S, Kalashnyk N, Riello M, Moreton B, Tasseroul J, Wouters J, Jones TS, De Vita A, Costantini G, Bonifazi D. Angew. Chem. Int. Ed. 2013; 52: 7410
• 27 Wiberg E, Bolz A. Chem. Ber. 1940; 73: 209
• 28 Wiberg E, Hertwig K, Bolz A. Z. Anorg. Allg. Chem. 1948; 256: 177
• 29 Schlesinger HI, Horvitz L, Burg AB. J. Am. Chem. Soc. 1936; 58: 407
• 30 Schlesinger HI, Ritter DM, Burg AB. J. Am. Chem. Soc. 1938; 60: 1296
• 31 Wideman T, Sneddon LG. Inorg. Chem. 1995; 34: 1002
• 32 Schaeffer GW, Anderson ER. J. Am. Chem. Soc. 1949; 71: 2143
• 33 Schaeffer GW, Schaeffer R, Schlesinger HI. J. Am. Chem. Soc. 1951; 73: 1612
• 34 Mikheeva VI, Markina VY. J. Inorg. Chem., USSR 1956; 56
• 35a Volkov VV, Myakishev KG. Khim. Interesakh Ustoich. Razvit. 2002; 10: 31
• 35b Volkov VV, Bagryantsev GI, Myakishev KG. Russ. J. Inorg. Chem. 1970; 15: 1510
• 36 Volkov VV, Myakishev KG, Ilinchik EA. Chem. Sustainable Dev. 2009; 17: 225
• 37 Brown CA, Laubengayer AW. J. Am. Chem. Soc. 1955; 77: 3699
• 38 Bernard S, Miele P. Materials 2014; 7: 7436
• 39 Jones RG, Kinney CR. J. Am. Chem. Soc. 1939; 61: 1378
• 40 Schaeffer R, Steindler M, Hohnstedt L, Smith HS, Eddy LB, Schlesinger HI. J. Am. Chem. Soc. 1954; 76: 3303
• 41 Hohnstedt LF, Haworth DT. J. Am. Chem. Soc. 1960; 82: 89
• 42 Dahl GH, Schaeffer R. J. Inorg. Nucl. Chem. 1960; 12: 380
• 43 Framery E, Vaultier M. Heteroat. Chem. 2000; 11: 218
• 44 Li J.-s, Zhang C.-r, Li B, Cao F, Wang S.-q. Eur. J. Inorg. Chem. 2010; 1763
• 45 Jaska CA, Temple K, Lough AJ, Manners I. Chem. Commun. 2001; 962
• 46 Jaska CA, Temple K, Lough AJ, Manners I. J. Am. Chem. Soc. 2003; 125: 9424
• 47 Vance JR, Robertson AP. M, Lee K, Manners I. Chem. Eur. J. 2011; 17: 4099
• 48a Lu Z, Schweighauser L, Hausmann H, Wegner HA. Angew. Chem. Int. Ed. 2015; 54: 15556
• 48b Wegner HA, Lu Z. EP 3081528A1, 2016
• 49 Bissot TC, Parry RW. J. Am. Chem. Soc. 1955; 77: 3481
• 50 Brydson R, Daniels H, Fox MA, Greatrex R, Workman C. Chem. Commun. 2002; 718
• 51 Nehate SD, Saikumar AK, Prakash A, Sundaram KB. Mater. Today Adv. 2020; 8: 100106
• 52 Meller A, Schaschel E. Inorg. Nucl. Chem. Lett. 1966; 2: 41
• 53 Paetzold P. Iminoboranes . In Advances in Inorganic Chemistry, Vol. 31. Emeléus HJ, Sharpe AG. Academic Press; New York: 1987: 123-170
• 54 Paetzold P. Phosphorus, Sulfur Silicon Relat. Elem. 1994; 93: 39
• 55 Emeléus HJ, Wade K. J. Chem. Soc. 1960; 2614
• 56 Jennings JR, Wade K. J. Chem. Soc. A 1968; 1946
• 57 Leffler AJ. Inorg. Chem. 1964; 3: 145
• 58 Pattison I, Wade K. J. Chem. Soc. A 1968; 842
• 59 Hough WV, Schaeffer GW, Dzurus M, Stewart AC. J. Am. Chem. Soc. 1955; 77: 864
• 60 Myakishev K, Il’inchik E, Volkov V. Chem. Sustainable Dev. 2008; 16: 197 ; https://sibran.ru/en/journals/KhUR/
• 61 Yamamoto Y, Miyamoto K, Umeda J, Nakatani Y, Yamamoto T, Miyaura N. J. Organomet. Chem. 2006; 691: 4909
• 62 Smalley JH, Stafiej SF. J. Am. Chem. Soc. 1959; 81: 582
• 63 Wiberg E, Hertwig K. Z. Anorg. Allg. Chem. 1947; 255: 141
• 64 Hahn J, Krieg M, Keck C, Maichle-Mössmer C, Fink RF, Bettinger HF. Dalton Trans. 2018; 47: 17304
• 65 Turner HS, Warne RJ. J. Chem. Soc. 1965; 6421
• 66 Emeléus HJ, Videla GJ. J. Chem. Soc. 1959; 1306
• 67 Rothgery EF, Hohnstedt LF. Inorg. Chem. 1967; 6: 1065
• 68 Nöth H, Sachdev H. Z. Naturforsch., B 1997; 52: 1345
• 69 Nöth H. Z. Naturforsch., B 1961; 16: 618
• 70 Deng C, Song YC, De Wang Y, Li YH, Lei YP, Cao SW. Chin. Chem. Lett. 2010; 21: 135
• 71 Sujishi S, Witz S. J. Am. Chem. Soc. 1957; 79: 2447
• 72 Reich TE, Jackson KT, Li S, Jena P, El-Kaderi HM. J. Mater. Chem. 2011; 21: 10629
• 73 Jackson KT, Rabbani MG, Reich TE, El-Kaderi HM. Polym. Chem. 2011; 2: 2775
• 74 Jackson KT, Reich TE, El-Kaderi HM. Chem. Commun. 2012; 48: 8823
• 75 Reich TE, Behera S, Jackson KT, Jena P, El-Kaderi HM. J. Mater. Chem. 2012; 22: 13524
• 76 Riensch NA, Deniz A, Kühl S, Müller L, Adams A, Pich A, Helten H. Polym. Chem. 2017; 8: 5264
• 77 Aubrey DW, Lappert MF. J. Chem. Soc. 1959; 2927
• 78 Becher HJ, Frick S. Z. Anorg. Allg. Chem. 1958; 295: 83
• 79 Fritz P, Niedenzu K, Dawson JW. Inorg. Chem. 1964; 3: 626
• 80 Brinckmann FE, Stone FG. A. J. Am. Chem. Soc. 1960; 82: 6218
• 81 Booth RB, Kraus CA. J. Am. Chem. Soc. 1952; 74: 1415
• 82 Gerrard W, Hudson HR, Mooney EF. J. Chem. Soc. 1962; 113
• 83 Nöth H, Troll A. Eur. J. Inorg. Chem. 2005; 3524
• 84 Nöth H, Rojas-Lima S, Troll A. Eur. J. Inorg. Chem. 2005; 1895
• 85 Hawthorne MF. J. Am. Chem. Soc. 1961; 83: 833
• 86 Hawthorne MF. J. Am. Chem. Soc. 1961; 83: 831
• 87 Mikhailov BM, Kozminskaya TK. Izv. Akad. Nauk SSSR, Ser. Khim. 1960; 2247
• 88 Blanchard C, Framery E, Vaultier M. Synthesis 1996; 45
• 89 Haberecht J, Krummland A, Breher F, Gebhardt B, Rüegger H, Nesper R, Grützmacher H. Dalton Trans. 2003; 2126
• 90 Seyferth D, Kogler HP, Freyer WR, Takamizawa M, Yamazaki H, Sato Y. Synthesis of B-Organofunctional Borazine Derivatives . In Advances in Chemistry, Vol. 42, Chap. 25. American Chemical Society; Washington DC: 1964: 259-265
• 91 Groszos SJ, Stafiej SF. J. Am. Chem. Soc. 1958; 80: 1357
• 92 Niedenzu K, Dawson JW. J. Am. Chem. Soc. 1959; 81: 3561
• 93 Brown JF. J. Am. Chem. Soc. 1952; 74: 1219
• 94 Lynch AT, Sneddon LG. J. Am. Chem. Soc. 1987; 109: 5867
• 95 Lynch AT, Sneddon LG. J. Am. Chem. Soc. 1989; 111: 6201
• 96 Sneddon LG, Su K, Fazen PJ, Lynch AT, Remsen EE, Beck JS. Polymeric Precursors to Boron Nitride Ceramics . In Inorganic and Organometallic Oligomers and Polymers . Harrod JF, Laine RM. Springer; Dordrecht: 1991: 199-208 , DOI: DOI: 10.1007/978-94-011-3214-5_15
• 97 Fazen PJ, Sneddon LG. Organometallics 1994; 13: 2867
• 98 Brennan GL, Dahl GH, Schaeffer R. J. Am. Chem. Soc. 1960; 82: 6248
• 99 Klapötke TM, Rusan M. Z. Naturforsch., B 2014; 69: 1241
• 100 Muszkat KA, Hill L, Kirson B. Israel J. Chem. 1963; 1: 27
• 101 Bradley MJ, Ryschkewitsch GE, Sisler HH. J. Am. Chem. Soc. 1959; 81: 2635
• 102 Toury B, Cornu D, Lecocq S, Miele P. Appl. Organomet. Chem. 2003; 17: 68
• 103 Paine RT, Koestle W, Borek TT, Wood GL, Pruss EA, Duesler EN, Hiskey MA. Inorg. Chem. 1999; 38: 3738
• 104 Niedenzu K, Beyer H, Jenne H. Chem. Ber. 1963; 96: 2649
• 105 Miller JM, Wilson GL. J. Fluorine Chem. 1974; 4: 207
• 106 Ryschkewitsch GE, Harris JJ, Sisler HH. J. Am. Chem. Soc. 1958; 80: 4515
• 107 Haworth DT, Hohnstedt LF. J. Am. Chem. Soc. 1960; 82: 3860
• 108 Pellon J, Deichert WG, Thomas WM. J. Polym. Sci. 1961; 55: 153
• 109 Oubaha H, Demitri N, Rault-Berthelot J, Dubois P, Coulembier O, Bonifazi D. J. Org. Chem. 2019; 84: 9101
• 110 Marinelli D, Fasano F, Najjari B, Demitri N, Bonifazi D. J. Am. Chem. Soc. 2017; 139: 5503
• 111 Seyferth D, Kögler HP. J. Inorg. Nucl. Chem. 1960; 15: 99
• 112 Cowley AH, Sisler HH, Ryschkewitsch GE. J. Am. Chem. Soc. 1960; 82: 501
• 113 Chang CW, Nabae Y, Kuroki S, Hayakawa T, Kakimoto M.-a, Miyata S. Chem. Lett. 2012; 41: 923
• 114 Kervyn S, Fenwick O, Di Stasio F, Shin YS, Wouters J, Accorsi G, Osella S, Beljonne D, Cacialli F, Bonifazi D. Chem. Eur. J. 2013; 19: 7771
• 115 Kervyn S, Nakanishi T, Aimi J, Saeki A, Seki S, Champagne B, Bonifazi D. Chem. Lett. 2012; 41: 1210
• 116 Wakamiya A, Ide T, Yamaguchi S. J. Am. Chem. Soc. 2005; 127: 14859
• 117 Niedenzu K, Dawson JW. Angew. Chem. 1959; 71: 651
• 118 Niedenzu K, Dawson JW. Angew. Chem. 1960; 72: 920
• 119 Stepanenko V, Ortiz-Marciales M, Barnes CE, Garcia C. Tetrahedron Lett. 2006; 47: 7603
• 120 Brotherton RJ, Steinberg H. J. Org. Chem. 1961; 26: 4632
• 121a Cragg RH, Weston AF. J. Chem. Soc., Chem. Commun. 1972; 79
• 121b Cragg RH, Weston AF. J. Chem. Soc., Dalton Trans. 1975; 93
• 122 Harris JJ, Rudner B. J. Org. Chem. 1962; 27: 3848
• 123 Limberti S, Emmett L, Trandafir A, Kociok-Köhn G, Pantoş GD. Chem. Sci. 2019; 10: 9565
• 124 Culling GC, Dewar MJ. S, Marr PA. J. Am. Chem. Soc. 1964; 86: 1125
• 125 Luo W, Zakharov LN, Liu S.-Y. J. Am. Chem. Soc. 2011; 133: 13006
• 126 Luo W, Campbell PG, Zakharov LN, Liu S.-Y. J. Am. Chem. Soc. 2011; 133: 19326
• 127 Biswas S, Müller M, Tönshoff C, Eichele K, Maichle-Mössmer C, Ruff A, Speiser B, Bettinger HF. Eur. J. Org. Chem. 2012; 2012: 4634
• 128 Köster R, Iwasaki K, Hattori S, Morita Y. Justus Liebigs Ann. Chem. 1968; 720: 23
• 129 Köster R, Hattori S, Morita Y. Angew. Chem. Int. Ed. 1965; 4: 695
• 130 Müller M, Maichle-Mössmer C, Sirsch P, Bettinger HF. ChemPlusChem 2013; 78: 988
• 131 Müller M, Behnle S, Maichle-Mössmer C, Bettinger HF. Chem. Commun. 2014; 50: 7821
• 132 Tönshoff C, Müller M, Kar T, Latteyer F, Chassé T, Eichele K, Bettinger HF. ChemPhysChem 2012; 13: 1173
• 133 Krieg M, Reicherter F, Haiss P, Ströbele M, Eichele K, Treanor M.-J, Schaub R, Bettinger HF. Angew. Chem. Int. Ed. 2015; 54: 8284
• 134 Sánchez-Sánchez C, Brüller S, Sachdev H, Müllen K, Krieg M, Bettinger HF, Nicolaï A, Meunier V, Talirz L, Fasel R, Ruffieux P. ACS Nano 2015; 9: 9228
• 135 Dosso J, Tasseroul J, Fasano F, Marinelli D, Biot N, Fermi A, Bonifazi D. Angew. Chem. Int. Ed. 2017; 56: 4483
• 136 Haworth DT, Hohnstedt LF. J. Am. Chem. Soc. 1959; 81: 842
• 137 Wagner RI, Bradford JL. Inorg. Chem. 1962; 1: 93
• 138 Gaines DF, Schaeffer R. J. Am. Chem. Soc. 1963; 85: 3592
• 139 Dahl GH, Schaeffer R. J. Am. Chem. Soc. 1961; 83: 3032
• 140 Riley RF, Schack CJ. Inorg. Chem. 1964; 3: 1651
• 141 Geri JB, Wade Wolfe MM, Szymczak NK. Angew. Chem. Int. Ed. 2018; 57: 1381
• 142 Seyferth D, Takamizawa M. J. Org. Chem. 1963; 28: 1142
• 143 Wagner RI, Bradford JL. Inorg. Chem. 1962; 1: 99
• 144 Chiavarino B, Crestoni ME, Marzio AD, Fornarini S, Rosi M. J. Am. Chem. Soc. 1999; 121: 11204
• 145 Lappert MF, Srivastava G. J. Chem. Soc. A 1967; 602
• 146 Fasano F, Dosso J, Bezzu CG, Carta M, Kerff F, Demitri N, Su B.-L, Bonifazi D. Chem. Eur. J. 2021; 27: 4124
• 147 Li N, Wu B, Yu C, Li T, Zhang W.-X, Xi Z. Angew. Chem. Int. Ed. 2020; 59: 8868
• 148 Gorman AD, Bailey JA, Fey N, Young TA, Sparkes HA, Pringle PG. Angew. Chem. Int. Ed. 2018; 57: 15802
• 149 Braunschweig H, Kollann C, Müller M. Eur. J. Inorg. Chem. 1998; 1998: 291
• 150 Webster CE, Fan Y, Hall MB, Kunz D, Hartwig JF. J. Am. Chem. Soc. 2003; 125: 858
• 151 Braunschweig H, Green H, Radacki K, Uttinger K. Dalton Trans. 2008; 3531
• 152 Anton K, Fußstetter H, Nöth H. Chem. Ber. 1981; 114: 2723
• 153 Gemünd B, Günther B, Nöth H. ARKIVOC 2008; (v): 136
• 154 Lisovenko AS, Timoshkin AY. Inorg. Chem. 2010; 49: 10357
• 155 Prinz R, Werner H. Angew. Chem. Int. Ed. 1967; 6: 91
• 156 Werner H, Prinz R, Deckelmann E. Chem. Ber. 1969; 102: 95
• 157 Adcock JL, Lagowski JJ. Inorg. Chem. 1973; 12: 2533
• 158 Scotti M, Werner H. J. Organomet. Chem. 1974; 81: C17
• 159 Bridgeman AJ. Polyhedron 1998; 17: 2279
• 160 Huttner G, Krieg B. Angew. Chem. Int. Ed. 1971; 10: 512