Facile Activation of Homoatomic σ Bonds in White Phosphorus and Diborane by a Diboraallene
Dr. Wei Lu
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorKai Xu
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
Search for more papers by this authorDr. Yongxin Li
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorCorresponding Author
Prof. Dr. Hajime Hirao
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Rei Kinjo
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorDr. Wei Lu
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorKai Xu
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
Search for more papers by this authorDr. Yongxin Li
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorCorresponding Author
Prof. Dr. Hajime Hirao
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Rei Kinjo
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore, 637371 Singapore
Search for more papers by this authorGraphical Abstract
Metal-free activation of homoatomic E−E σ bonds (E=P, B) in white phosphorus (P4) and bis(catecholato)diboron (B2cat2) with a 1,2-diboraallene is reported. The former affords BnP4 cages (n=2, 4), whereas the latter leads to the formation of a tetraborane featuring a B4 chain through homonuclear catenation.
Abstract
Metal-free activation of homoatomic E−E σ bonds (E=P, B) in white phosphorus (P4) and bis(catecholato)diboron (B2cat2) with a 1,2-diboraallene 1 is reported. The 1:1 and 1:2 reactions of P4 with 1 afford BnP4 cages (2: n=2, 3: n=4), whereas a stoichiometric mixture of 1 and B2cat2 undergoes homonuclear catenation through the addition of the B−B σ bond of B2cat2 across the B=B double bond of 1 (i.e. diboration), which leads to the formation of a tetraborane (4) featuring a B4 chain.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| anie201808357-sup-0001-misc_information.pdf2 MB | Supplementary |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1
- 1aY. Wang, B. Quillian, P. Wei, C. S. Wannere, Y. Xie, R. B. King, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2007, 129, 12412–12413;
- 1bD. Scheschkewitz, Angew. Chem. Int. Ed. 2008, 47, 1995–1997; Angew. Chem. 2008, 120, 2021–2023;
- 1cY. Wang, B. Quillian, P. Wei, Y. Xie, C. S. Wannere, R. B. King, H. F. Schaefer III, P. v. R. Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2008, 130, 3298–3299;
- 1dY. Wang, G. H. Robinson, Inorg. Chem. 2011, 50, 12326–12337;
- 1eY. Wang, G. H. Robinson, Inorg. Chem. 2014, 53, 11815–11832.
- 2
- 2aM. P. Mitoraj, A. Michalak, Inorg. Chem. 2011, 50, 2168–2174;
- 2bH. Braunschweig, R. D. Dewhurst, Angew. Chem. Int. Ed. 2013, 52, 3574–3583; Angew. Chem. 2013, 125, 3658–3667;
- 2cJ. Brand, H. Braunschweig, S. S. Sen, Acc. Chem. Res. 2014, 47, 180–191;
- 2dH. Braunschweig, R. D. Dewhurst, Organometallics 2014, 33, 6271–6277;
- 2eM. Arrowsmith, H. Braunschweig, T. E. Stennett, Angew. Chem. Int. Ed. 2017, 56, 96–115; Angew. Chem. 2017, 129, 100–120.
- 3For diborenes in the coordination sphere of transition metals, see:
- 3aH. Braunschweig, A. Damme, R. D. Dewhurst, A. Vargas, Nat. Chem. 2013, 5, 115–121;
- 3bN. Arnold, H. Braunschweig, R. D. Dewhurst, W. C. Ewing, J. Am. Chem. Soc. 2016, 138, 76–79;
- 3cB. Mondal, R. Bag, S. Ghorai, K. Bakthavachalam, E. D. Jemmis, S. Ghosh, Angew. Chem. Int. Ed. 2018, 57, 8079–8083; Angew. Chem. 2018, 130, 8211–8215.
- 4
- 4aH. Braunschweig, I. Krummenacher, C. Lichtenberg, J. D. Mattock, M. Schäfer, U. Schmidt, C. Schneider, T. Steffenhagen, S. Ullrich, A. Vargas, Angew. Chem. Int. Ed. 2017, 56, 889–892; Angew. Chem. 2017, 129, 907–911;
- 4bH. Braunschweig, P. Constantinidis, T. Dellermann, W. C. Ewing, I. Fischer, M. Hess, F. R. Knight, A. Rempel, C. Schneider, S. Ullrich, A. Vargas, J. D. Woollins, Angew. Chem. Int. Ed. 2016, 55, 5606–5609; Angew. Chem. 2016, 128, 5697–5700;
- 4cP. Bissinger, H. Braunschweig, M. A. Celik, C. Claes, R. D. Dewhurst, S. Endres, H. Kelch, T. Kramer, I. Krummenacher, C. Schneider, Chem. Commun. 2015, 51, 15917–15920.
- 5H. Braunschweig, R. D. Dewhurst, K. Hammond, J. Mies, K. Radacki, A. Vargas, Science 2012, 336, 1420–1422.
- 6J. Böhnke, H. Braunschweig, W. C. Ewing, C. Hörl, T. Kramer, I. Kummenacher, J. Mies, A. Vargas, Angew. Chem. Int. Ed. 2014, 53, 9082–9085; Angew. Chem. 2014, 126, 9228–9231.
- 7R. Bertermann, H. Braunschweig, P. Constantinidis, T. Dellermann, R. D. Dewhurst, W. C. Ewing, I. Fischer, T. Kramer, J. Mies, A. K. Phukan, A. Vargas, Angew. Chem. Int. Ed. 2015, 54, 13090–13094; Angew. Chem. 2015, 127, 13282–13286.
- 8
- 8aP. Bissinger, H. Braunschweig, A. Damme, T. Kupfer, A. Vargas, Angew. Chem. Int. Ed. 2012, 51, 9931–9934; Angew. Chem. 2012, 124, 10069–10073;
- 8bP. Bissinger, A. Steffen, A. Vargas, R. D. Dewhurst, A. Damme, H. Braunschweig, Angew. Chem. Int. Ed. 2015, 54, 4362–4366; Angew. Chem. 2015, 127, 4436–4440;
- 8cH. Braunschweig, T. Dellermann, R. D. Dewhurst, B. Hupp, T. Kramer, J. D. Mattock, J. Mies, A. K. Phukan, A. Steffen, A. Vargas, J. Am. Chem. Soc. 2017, 139, 4887–4893;
- 8dS. R. Wang, M. Arrowsmith, H. Braunschweig, R. D. Dewhurst, M. Dömling, J. D. Mattock, C. Pranckevicius, A. Vargas, J. Am. Chem. Soc. 2017, 139, 10661–10664.
- 9
- 9aP. Bissinger, H. Braunschweig, A. Damme, T. Kupfer, I. Krummenacher, A. Vargas, Angew. Chem. Int. Ed. 2014, 53, 5689–5693; Angew. Chem. 2014, 126, 5797–5801;
- 9bP. Bissinger, H. Braunschweig, A. Damme, C. Hörl, I. Krummenacher, T. Kupfer, Angew. Chem. Int. Ed. 2015, 54, 359–362; Angew. Chem. 2015, 127, 366–369.
- 10M. Arrowsmith, J. Böhnke, H. Braunschweig, M. A. Celik, C. Claes, W. C. Ewing, I. Krummenacher, K. Lubitz, C. Schneider, Angew. Chem. Int. Ed. 2016, 55, 11271–11275; Angew. Chem. 2016, 128, 11441–11445.
- 11
- 11aH. Braunschweig, T. Dellermann, R. D. Dewhurst, W. C. Ewing, K. Hammond, J. O. C. Jimenez-Halla, T. Kramer, I. Krummenacher, J. Mies, A. K. Phukan, A. Vargas, Nat. Chem. 2013, 5, 1025–1028;
- 11bJ. Böhnke, H. Braunschweig, T. Dellermann, W. C. Ewing, K. Hammond, T. Kramer, J. O. C. Jimenez-Halla, J. Mies, Angew. Chem. Int. Ed. 2015, 54, 13801–13805; Angew. Chem. 2015, 127, 14006–14010;
- 11cM. Arrowsmith, J. Böhnke, H. Braunschweig, M. A. Celik, Angew. Chem. Int. Ed. 2017, 56, 14287–14292; Angew. Chem. 2017, 129, 14475–14480.
- 12A. Stoy, J. Böhnke, J. O. C. Jimenéz-Halla, R. D. Dewhurst, T. Thiess, H. Braunschweig, Angew. Chem. Int. Ed. 2018, 57, 5947–5951; Angew. Chem. 2018, 130, 6055–6059.
- 13J. Böhnke, H. Braunschweig, T. Dellermann, W. C. Ewing, T. Kramer, I. Krummenacher, A. Vargas, Angew. Chem. Int. Ed. 2015, 54, 4469–4473; Angew. Chem. 2015, 127, 4551–4555.
- 14
- 14aH. Braunschweig, T. Dellermann, W. C. Ewing, T. Kramer, C. Schneider, S. Ullrich, Angew. Chem. Int. Ed. 2015, 54, 10271–10275; Angew. Chem. 2015, 127, 10409–10413;
- 14bS. R. Wang, M. Arrowsmith, J. Böhnke, H. Braunschweig, T. Dellermann, R. D. Dewhurst, H. Kelch, I. Krummenacher, J. D. Mattock, J. H. Müssig, T. Thiess, A. Vargas, J. Zhang, Angew. Chem. Int. Ed. 2017, 56, 8009–8013; Angew. Chem. 2017, 129, 8122–8126.
- 15M. Arrowsmith, J. Böhnke, H. Braunschweig, M. A. Celik, T. Dellermann, K. Hammond, Chem. Eur. J. 2016, 22, 17169–17172.
- 16
- 16aH. Braunschweig, R. D. Dewhurst, C. Hörl, A. K. Phukan, F. Pinzner, S. Ullrich, Angew. Chem. Int. Ed. 2014, 53, 3241–3244; Angew. Chem. 2014, 126, 3305–3308;
- 16bH. Braunschweig, C. Hörl, Chem. Commun. 2014, 50, 10983–10985.
- 17W. Lu, Y. Li, R. Ganguly, R. Kinjo, J. Am. Chem. Soc. 2017, 139, 5047–5050.
- 18T. E. Stennett, J. D. Mattock, I. Vollert, A. Vargas, H. Braunschweig, Angew. Chem. Int. Ed. 2018, 57, 4098–4102.
- 19
- 19aW. Lu, Y. Li, R. Ganguly, R. Kinjo, Angew. Chem. Int. Ed. 2017, 56, 9829–9832; Angew. Chem. 2017, 129, 9961–9964;
- 19bW. Lu, Y. Li, R. Ganguly, R. Kinjo, J. Am. Chem. Soc. 2018, 140, 1255–1258;
- 19cW. Lu, R. Kinjo, Chem. Commun. 2018, 54, 8842–8844;
- 19dW. Lu, R. Kinjo, Chem. Eur. J. 2018, 24, 15656–15662; Very recently, the Braunschweig group has reported the splitting of H2 with zerovalent sp-sp2 diboron compound. See:
- 19eJ. Böhnke, M. Arrowsmith, H. Braunschweig, J. Am. Chem. Soc. 2018, 140, 10368–10373.
- 20
- 20aM. Scheer, G. Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236–4256;
- 20bN. A. Giffin, J. D. Masuda, Coord. Chem. Rev. 2011, 255, 1342–1359;
- 20cS. Khan, S. S. Sen, H. W. Roesky, Chem. Commun. 2012, 48, 2169–2179;
- 20dM. H. Holthausen, J. J. Weigand, Chem. Soc. Rev. 2014, 43, 6639–6657;
- 20eJ. E. Borger, A. W. Ehlers, J. C. Slootweg, K. Lammertsma, Chem. Eur. J. 2017, 23, 11738–11746;
- 20fT. Chu, G. I. Nikonov, Chem. Rev. 2018, 118, 3608–3680.
- 21
- 21aJ. D. Masuda, W. W. Schoeller, B. Donnadieu, G. Bertrand, Angew. Chem. Int. Ed. 2007, 46, 7052–7055; Angew. Chem. 2007, 119, 7182–7185;
- 21bJ. D. Masuda, W. W. Schoeller, B. Donnadieu, G. Bertrand, J. Am. Chem. Soc. 2007, 129, 14180–14181;
- 21cC. D. Martin, C. M. Weinstein, C. E. Moore, A. L. Rheingold, G. Bertrand, Chem. Commun. 2013, 49, 4486–4488.
- 22
- 22aY. Peng, H. J. Fan, H. P. Zhu, H. W. Roesky, J. Magull, C. E. Hughes, Angew. Chem. Int. Ed. 2004, 43, 3443–3445; Angew. Chem. 2004, 116, 3525–3527;
- 22bY. Xiong, S. Yao, M. Brym, M. Driess, Angew. Chem. Int. Ed. 2007, 46, 4511–4513; Angew. Chem. 2007, 119, 4595–4597;
- 22cG. Prabusankar, A. Doddi, C. Gemel, M. Winter, R. A. Fischer, Inorg. Chem. 2010, 49, 7976–7980;
- 22dS. Khan, R. Michel, S. S. Sen, H. W. Roesky, D. Stalke, Angew. Chem. Int. Ed. 2011, 50, 11786–11789; Angew. Chem. 2011, 123, 11990–11993;
- 22eF. Dielmann, G. Bertrand, Chem. Eur. J. 2015, 21, 191–198;
- 22fI. Alvarado-Beltran, A. Baceiredo, N. Saffon-Merceron, V. Branchadell, T. Kato, Angew. Chem. Int. Ed. 2016, 55, 16141–16144; Angew. Chem. 2016, 128, 16375–16378;
- 22gC. M. E. Graham, C. L. B. Macdonald, P. P. Power, Z. D. Brown, P. J. Ragogna, Inorg. Chem. 2017, 56, 9111–9119.
- 23
- 23aA. R. Fox, R. J. Wright, E. Rivard, P. P. Power, Angew. Chem. Int. Ed. 2005, 44, 7729–7733; Angew. Chem. 2005, 117, 7907–7911;
- 23bS. Khan, R. Michel, J. M. Dieterich, R. A. Mata, H. W. Roesky, J.-P. Demers, A. Lange, D. Stalke, J. Am. Chem. Soc. 2011, 133, 17889–17894;
- 23cS. S. Sen, S. Khan, H. W. Roesky, D. Kratzert, K. Meindl, J. Henn, D. Stalke, J.-P. Demers, A. Lange, Angew. Chem. Int. Ed. 2011, 50, 2322–2325; Angew. Chem. 2011, 123, 2370–2373.
- 24M. Driess, A. D. Fanta, D. R. Powell, R. West, Angew. Chem. Int. Ed. Engl. 1989, 28, 1038–1040; Angew. Chem. 1989, 101, 1087–1088.
- 25
- 25aR. Dinda, O. Ciobanu, H. Wadepohl, O. Hübner, R. Acharyya, H.-J. Himmel, Angew. Chem. Int. Ed. 2007, 46, 9110–9113; Angew. Chem. 2007, 119, 9270–9273;
- 25bL. Kong, W. Lu, Y. Li, R. Ganguly, R. Kinjo, J. Am. Chem. Soc. 2016, 138, 8623–8629.
- 26
- 26aA. Rosas-Sánchez, I. Alvarado-Beltran, A. Baceiredo, D. Hashizume, N. Saffon-Merceron, V. Branchadell, T. Kato, Angew. Chem. Int. Ed. 2017, 56, 4814–4818; Angew. Chem. 2017, 129, 4892–4896;
- 26bS. J. Geier, T. M. Gilbert, D. W. Stephan, Inorg. Chem. 2011, 50, 336–344;
- 26cR. A. Bartlett, H. V. R. Dias, X. Feng, P. P. Power, J. Am. Chem. Soc. 1989, 111, 1306–1311.
- 27
- 27aM. B. Power, A. R. Barron, Angew. Chem. Int. Ed. Engl. 1991, 30, 1353–1354; Angew. Chem. 1991, 103, 1403–1404;
- 27bM. H. Holthausen, C. Richter, A. Hepp, J. J. Weigand, Chem. Commun. 2010, 46, 6921–6923;
- 27cJ. E. Borger, A. W. Ehlers, M. Lutz, J. C. Slootweg, K. Lammertsma, Angew. Chem. Int. Ed. 2016, 55, 613–617; Angew. Chem. 2016, 128, 623–627.
- 28
- 28aH. A. Beall, W. N. Lipscomb, Inorg. Chem. 1967, 6, 874–879;
- 28bİ. Muz, M. Atiş, Inorg. Chim. Acta 2016, 453, 626–632.
- 29
- 29aE. C. Neeve, S. J. Geier, I. A. I. Mkhalid, S. A. Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091–9161;
- 29bA. B. Cuenca, R. Shishido, H. Ito, E. Fernández, Chem. Soc. Rev. 2017, 46, 415–430.
- 30H. Braunschweig, R. D. Dewhurst, S. Mozo, ChemCatChem 2015, 7, 1630–1638.
- 31
- 31aH. Braunschweig, Q. Ye, A. Vargas, R. D. Dewhurst, K. Radacki, A. Damme, Nat. Chem. 2012, 4, 563–567;
- 31bA. Hermann, J. Cid, J. D. Mattock, R. D. Dewhurst, I. Krummenacher, A. Vargas, M. J. Ingleson, H. Braunschweig, Angew. Chem. Int. Ed. 2018, 57, 10091–10095; Angew. Chem. 2018, 130, 10248–10252.
- 32
- 32aW. Clegg, C. Dai, F. J. Lawlor, T. B. Marder, P. Nguyen, N. C. Norman, N. L. Pickett, W. P. Power, A. J. Scott, J. Chem. Soc. Dalton Trans. 1997, 839–846;
- 32bH. Braunschweig, A. Damme, R. D. Dewhurst, T. Kramer, T. Kupfer, K. Radacki, E. Siedler, A. Trumpp, K. Wagner, C. Werner, J. Am. Chem. Soc. 2013, 135, 8702–8707.
- 33A. Moezzi, M. M. Olmstead, R. A. Bartlett, P. P. Power, Organometallics 1992, 11, 2383–2388.
