Skip to content
Publicly Available Published by De Gruyter April 29, 2013

New ligand platforms featuring boron-rich clusters as organomimetic substituents

  • Alexander M. Spokoyny

200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boron-rich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the “space race” while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules—a phenomenon best described as “organomimetic”. Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion.

References

1 A. Stock. Hydrides of Boron and Silicon (The George Fisher Baker Non-Resident Lectureship in Chemistry at Cornell University), Cornell University Press, Ithaca, NY (1933).Search in Google Scholar

2 10.1016/S0277-5387(00)88023-7, W. H. Brock, K. H. Jensen, C. K. Jørgensen. Polyhedron2, 1 (1983).Search in Google Scholar

3a W. N. Lipscomb. The Boranes and Their Relatives, Nobel Lecture, December 11, 1976.Search in Google Scholar

3b E. Muetterties. Boron Hydride Chemistry, Academic Press, New York (1975).Search in Google Scholar

4 10.1021/cr960366n, M. Ephritikhine. Chem. Rev.97, 2193 (1997).Search in Google Scholar PubMed

5 10.1021/ja01097a049, H. I. Schlesinger, H. C. Brown, B. Abraham, A. C. Bond, N. Davidson, A. E. Finholt, J. R. Gilbreath, H. Hoekstra, L. Horvitz, E. K. Hyde, J. J. Katz, J. Knight, R. A. Lad, D. L. Mayfield, L. Rapp, D. M. Ritter, A. M. Schwartz, I. Sheft, L. D. Tuck, A. O. Walker. J. Am. Chem. Soc.75, 186 (1953).Search in Google Scholar

6 10.1021/jo01360a626, H. C. Brown, B. C. Rao. J. Org. Chem.22, 1137 (1957).Search in Google Scholar

7 Biographical Memoirs of the National Academy of Sciences, Vol. 64, pp. 368–396, The National Academies Press, Washington, DC (1994).Search in Google Scholar

8 R. Grimes. Carboranes, 2nd ed., Elsevier (2011).10.1016/B978-0-12-374170-7.00014-8Search in Google Scholar

9 Original synthesis.Search in Google Scholar

9a 10.1021/ja01497a069, A. R. Pitochelli, M. F. Hawthorne. J. Am. Chem. Soc.82, 3228 (1960); recently optimized process amenable to laboratory synthesis.Search in Google Scholar

9b 10.1039/b821030f, V. Geis, K. Guttsche, H. Scherer, R. Uzun. Dalton Trans. 2687 (2009).Search in Google Scholar PubMed

10 R. N. Grimes. Metal Interactions with Boron Clusters, Plenum Press, New York (1982).10.1007/978-1-4899-2154-3Search in Google Scholar

11 10.1021/ic50010a002, Original synthesis: T. L. Heying, J. W. Ager Jr., S. L. Clark, D. J. Mangold, H. L. Goldstein, M. Hillman, R. J. Polak, J. W. Szymanski. Inorg. Chem.2, 1089 (1963).Search in Google Scholar

12 10.1021/cr200038x, M. Scholz, E. Hey-Hawkins. Chem. Rev.111, 7035 (2011).Search in Google Scholar PubMed

13 10.1039/c1nj20228f, B. P. Dash, R. Satapathy, J. A. Maguire, N. S. Hosmane. New J. Chem.35, 1955 (2011).Search in Google Scholar

14 10.1021/cr2000866, F. Issa, M. Kassiou, L. M. Rendina. Chem. Rev.111, 5701 (2011).Search in Google Scholar PubMed

15 Review article (see references within):Search in Google Scholar

15a A. Kraft. Bull. Hist. Chem.33, 61 (2008);10.1557/mrs2008.16Search in Google Scholar

15b 10.1021/ic50177a008, structural study (see references within): H. J. Buser, D. Schwarzenbach, W. Petter, A. Ludi. Inorg. Chem.16, 2704 (1977).Search in Google Scholar

16a E. Frankland. Experimental Researches in Pure, Applied and Physical Chemistry, John Van Voorst, London (1877).Search in Google Scholar

16b 10.1021/om010439f, D. Seyferth. Organometallics20, 2940 (2001).Search in Google Scholar

17 10.1021/ja00904a052, D. F. Shriver. J. Am. Chem. Soc.85, 3509 (1963).Search in Google Scholar

18 10.1021/ja01057a014, G. W. Parshall. J. Am. Chem. Soc.86, 361 (1964).Search in Google Scholar

19a J. S. Merola, J. R. Knorr. Abstracts of Papers, 199th National Meeting of the American Chemical Society, Boston, MA; American Chemical Society, Washington, DC (1990); INOR 392.Search in Google Scholar

19b 10.1021/om00162a002, J. R. Knorr, J. S. Merola. Organometallics9, 3008 (1990).Search in Google Scholar

19c 10.1021/ja00181a055, R. T. Baker, D. W. Ovenall, J. C. Calabrese, S. A. Westcott, N. J. Taylor, I. D. Williams, T. B. Marder. J. Am. Chem. Soc.112, 9399 (1990).Search in Google Scholar

20 R. H. Crabtree. The Organometallic Chemistry of the Transition Metals, 3rd ed., John Wiley (2001).Search in Google Scholar

21 10.1021/cr900333n, H. Braunschweig, R. D. Dewhurst, A. Schneider. Chem. Rev.110, 3924 (2010).Search in Google Scholar PubMed

22 10.1126/science.1186028, H. Braunschweig, K. Radacki, A. Schneider. Science328, 345 (2010).Search in Google Scholar PubMed

23 10.1126/science.7384796, J. A. Ibers, R. H. Holm. Science209, 223 (1980).Search in Google Scholar PubMed

24a 10.1021/i260020a006, M. M. Fein, J. E. Paustian, M. Sarakwash. Ind. Eng. Chem. Proc. Des. Dev.5, 380 (1966).Search in Google Scholar

24b 10.1021/i260014a001, M. M. Fein, J. E. Paustian. Ind. Eng. Chem. Proc. Des. Dev.4, 129 (1965).Search in Google Scholar

24c 10.1021/ic50086a039, J. F. Ditter, E. B. Klusmann, J. D. Oakes, R. D. Williams. Inorg. Chem.9, 889 (1970).Search in Google Scholar

25 10.1021/i360020a008, S. Papetti, C. Obenland, T. L. Heying. Ind. Eng. Chem. Prod. Res. Dev.5, 334 (1966).Search in Google Scholar

26a 10.1039/c29710000792, K. Wade. J. Chem. Soc. D 792 (1971).Search in Google Scholar

26b D. M. P. Mingos. Nature236, 99 (1972).10.1038/physci236099a0Search in Google Scholar

26c 10.1039/c3cc00069a, A. J. Welch. Chem. Commun.49, 3615 (2013).Search in Google Scholar PubMed

27 10.1021/ja01006a006, M. F. Hawthorne, D. C. Young, P. M. Garrett, D. A. Owen, S. Schwerin, F. N. Tebbe, P. A. Wegner. J. Am. Chem. Soc.90, 862 (1968).Search in Google Scholar

28 B–C bond formation:Search in Google Scholar

28a 10.1016/S0022-328X(00)83405-1, L. I. Zakharkin, A. I. Kovredov, V. A. Olshevskaya, Z. S. Shaungumbekova. J. Organomet. Chem.226, 217 (1982);Search in Google Scholar

28b 10.1021/om9001044, B–O bond formation: K. Z. Kabytaev, S. N. Mukhin, I. V. Glukhov, Z. A. Starikova, V. I. Bregadze, I. P. Beletskaya. Organometallics28, 4758 (2009);Search in Google Scholar

28c 10.1021/om800635d, B–N bond formation: S. N. Mukhin, K. Z. Kabytaev, G. G. Zhigareva, I. V. Glukhov, Z. A. Starikova, V. I. Bregadze, I. P. Beletskaya. Organometallics27, 5937 (2008).Search in Google Scholar

29 10.1021/ja01086a053, M. F. Hawthorne, D. C. Young, P. A. Wegner. J. Am. Chem. Soc.87, 1818 (1965).Search in Google Scholar

30 10.1126/science.178.4060.462, M. F. Hawthorne, G. B. Dunks. Science178, 462 (1972).Search in Google Scholar

31 10.1002/chem.200304970, I. Rojo, F. Teixidor, C. Vi?as, R. Kivekäs, R. Sillanpää. Chem.—Eur. J.9, 4311 (2003).Search in Google Scholar

32a P. González-Cardoso, A. Stoica, P. Farràs, A. Pepiol, C. Viñas, F. Teixidor. Chem.—Eur. J.16, 6660 (2010).Search in Google Scholar

32b 10.1002/anie.201105668, A. Pepiol, F. Teixidor, R. Sillanpää, M. Lupu, C. Viñas. Angew. Chem., Int. Ed.50, 12491 (2011).Search in Google Scholar

33 10.1016/S0022-328X(00)00610-0, I. B. Sivaev, V. I. Bregadze. J. Organomet. Chem.614–615, 27 (2000).Search in Google Scholar

34 10.1021/ja100396n, T. C. Li, A. M. Spokoyny, C. She, O. K. Farha, C. A. Mirkin, T. J. Marks, J. T. Hupp. J. Am. Chem. Soc.132, 4580 (2010).Search in Google Scholar PubMed

35 10.1038/353737a0, B. O’Regan, M. Grätzel. Nature353, 737 (1991).Search in Google Scholar

36 10.1039/b809672d, T. W. Hamann, R. A. Jensen, A. B. F. Martinson, H. Van Ryswyk, J. T. Hupp. Energy Environ. Sci.1, 66 (2008).Search in Google Scholar

37 10.1021/jp112139h, T. C. Li, F. Fabregat-Santiago, O. K. Farha, A. M. Spokoyny, S. R. Raga, J. Bisquert, C. A. Mirkin, T. J. Marks, J. T. Hupp. J. Phys. Chem. C115, 11257 (2011).Search in Google Scholar

38 10.1002/anie.201002181, A. M. Spokoyny, T. C. Li, O. K. Farha, C. W. Machan, C. She, T. J. Marks, J. T. Hupp, C. A. Mirkin. Angew. Chem., Int. Ed.49, 5339 (2010).Search in Google Scholar PubMed

39 10.1021/ja00781a070, K. Tamao, Y. Kiso, K. Sumitani, M. Kumada. J. Am. Chem. Soc.94, 9268 (1972).Search in Google Scholar

40 10.1016/j.ccr.2004.01.002, G.-X. Jin. Coord. Chem. Rev.248, 587 (2004).Search in Google Scholar

41 10.1021/ja108051u, P. Dröse, C. G. Hrib, F. T. Edelmann. J. Am. Chem. Soc.132, 15540 (2010).Search in Google Scholar PubMed

42 10.1021/ja8067098, D. Liu, L. Dang, Y. Sun, H.-S. Chan, Z. Lin, Z. Xie. J. Am. Chem. Soc.130, 16103 (2008).Search in Google Scholar PubMed

43 10.1021/om8006344, H. Shen, H.-S. Chan, Z. Xie. Organometallics27, 5309 (2008).Search in Google Scholar

44 10.1021/om010642a, H. Wang, Y. Wang, H.-W. Li, Z. Xie. Organometallics20, 5110 (2001).Search in Google Scholar

45 10.1021/om0493356, X. Wang, G.-X. Jin. Organometallics23, 6319 (2004).Search in Google Scholar

46 10.1021/cr60216a001, H. Heaney. Chem. Rev.62, 81 (1962).Search in Google Scholar

47 10.1021/ja01584a024, J. D. Roberts, D. A. Semenow, H. E. Simmons Jr., L. A. Carlsmith. J. Am. Chem. Soc.78, 601 (1956).Search in Google Scholar

48 10.1021/ja00166a080, H. L. Gingrich, T. Ghosh, Q. Huang, M. Jones Jr. J. Am. Chem. Soc.112, 4082 (1990).Search in Google Scholar

49 10.1021/ja061605j, L. Deng, H.-S. Chan, Z. Xie. J. Am. Chem. Soc.128, 7728 (2006).Search in Google Scholar PubMed

50 10.1021/ar100156f, Z. Qiu, S. Ren, Z. Xie. Acc. Chem. Res.44, 299 (2011).Search in Google Scholar PubMed

51 10.1021/ja053050i, H. Jude, H. Disteldorf, S. Fischer, T. Wedge, A. M. Hawkridge, A. M. Arif, M. F. Hawthorne, D. C. Muddiman, P. J. Stang. J. Am. Chem. Soc.127, 12131 (2005).Search in Google Scholar PubMed

52 10.1039/b903811f, J. R. Long, O. M. Yaghi. Chem. Soc. Rev.38, 1213 (2009) and refs. Cited within.Search in Google Scholar PubMed

53 10.1021/ar1000617, O. K. Farha, J. T. Hupp. Acc. Chem. Res.43, 1166 (2010).Search in Google Scholar PubMed

54 10.1021/ja076167a, O. K. Farha, A. M. Spokoyny, K. L. Mulfort, M. F. Hawthorne, C. A. Mirkin, J. T. Hupp. J. Am. Chem. Soc.129, 12680 (2007).Search in Google Scholar PubMed

55 10.1039/b805785k, Y.-S. Bae, O. K. Farha, A. M. Spokoyny, C. A. Mirkin, J. T. Hupp, R. Q. Snurr. Chem. Commun. 4135 (2008).Search in Google Scholar PubMed

56 10.1002/smll.200900085, O. K. Farha, A. M. Spokoyny, K. L. Mulfort, S. Galli, J. T. Hupp, C. A. Mirkin. Small5, 1727 (2009).Search in Google Scholar PubMed

57 10.1039/b927499e, Y.-S. Bae, A. M. Spokoyny, O. K. Farha, R. Q. Snurr, J. T. Hupp, C. A. Mirkin. Chem. Commun.46, 3478 (2010).Search in Google Scholar PubMed

58 10.1002/cplu.201100083, S.-L. Huang, Y.-J. Lin, W.-B. Yu, G.-X. Jin. ChemPlusChem77, 141 (2012).Search in Google Scholar

59 10.1039/c2dt30708a, S.-L. Huang, L.-H. Weng, G.-X. Jin. Dalton Trans.41, 11657 (2012).Search in Google Scholar PubMed

60 10.1021/ja00050a096, J. Müeller, K. Ba?e, T. F. Magnera, J. Michl. J. Am. Chem. Soc.114, 9721 (1992).Search in Google Scholar

61 10.1016/j.ica.2010.08.007, A. M. Spokoyny, O. K. Farha, K. L. Mulfort, J. T. Hupp, C. A. Mirkin. Inorg. Chim. Acta364, 266 (2010).Search in Google Scholar

62a 10.1021/ja00855a017, E. L. Hoel, M. F. Hawthorne. J. Am. Chem. Soc.97, 6388 (1975).Search in Google Scholar

62b 10.1021/ja00154a038, Z. Zheng, M. Diaz, C. B. Knobler, M. F. Hawthorne. J. Am. Chem. Soc.117, 12338 (1995).Search in Google Scholar

62c V. N. Kalinin, A. V. Usatov, L. I. Zakharkin. Proc. Indian Natl. Sci. Acad.55, 293 (1989).Search in Google Scholar

63 D. Morales-Morales, C. M. Jensen. The Chemistry of Pincer Compounds, Elsevier (2007).Search in Google Scholar

64 10.1021/ja808893g, C. Gunanathan, L. J. W. Shimon, D. Milstein. J. Am. Chem. Soc.131, 3146 (2009).Search in Google Scholar PubMed

65 10.1126/science.1109389, J. Zhao, A. S. Goldman, J. F. Hartwig. Science307, 1080 (2005).Search in Google Scholar PubMed

66 10.1002/anie.200351320, G. Lin, N. D. Jones, R. A. Gossage, R. McDonald, R. G. Cavell. Angew. Chem., Int. Ed.42, 4054 (2003).Search in Google Scholar

67 10.1021/ja902526k, A. M. Spokoyny, M. G. Reuter, C. L. Stern, M. A. Ratner, T. Seidman, C. A. Mirkin. J. Am. Chem. Soc.131, 9482 (2009).Search in Google Scholar

68 10.1002/anie.200904795, J. I. Van der Vlugt. Angew Chem., Int. Ed.49, 252 (2010).Search in Google Scholar

69 10.1021/ic2002095, M. H. El-Zaria, H. Arii, H. Nakamura. Inorg. Chem.50, 4149 (2011).Search in Google Scholar

70 10.1126/science.1131914, Y. Segawa, M. Yamashita, K. Nozaki. Science314, 113 (2006).Search in Google Scholar

71 10.1021/ja9037092, Y. Segawa, M. Yamashita, K. Nozaki. J. Am. Chem. Soc.131, 9201 (2009).Search in Google Scholar

72 10.1039/c2dt31892j, H. Ogawa, M. Yamashita. Dalton Trans.45, 625 (2013).Search in Google Scholar

73 10.1021/cr60307a002, C. A. Tolman. Chem. Rev.77, 313 (1977).Search in Google Scholar

74 10.1038/nchem.1088, A. M. Spokoyny, C. W. Machan, D. C. Clingerman, M. S. Rosen, M. J. Wiester, R. D. Kennedy, A. A. Sarjeant, C. L. Stern, C. A. Mirkin. Nat. Chem.3, 590 (2011).Search in Google Scholar

75 10.1016/0022-5088(79)90096-1, J. Plešek, S. Heřmánek, B. Štíbr. J. Less Common Met.67, 225 (1979).Search in Google Scholar

76 10.1021/ja052981r, F. Teixidor, G. Barberà, A. Vaca, R. Kivekäs, R. Sillanpää, J. Oliva, C. Viñas. J. Am. Chem. Soc.127, 10158 (2005).Search in Google Scholar PubMed

77a 10.1021/om301116x, A. M. Spokoyny, C. D. Lewis, G. Teverovskiy, S. L. Buchwald. Organometallics31, 8478 (2012).Search in Google Scholar PubMed PubMed Central

77b V. Ts. Kampel, V. I. Bregadze, L. V. Ermanson, V. A. Antonovich, E. I. Matrosov, N. N. Godovikov, M. I. Kabachnik. Metalloorg. Khim.5, 1024 (1992).Search in Google Scholar

77c A. I. Yanovskii, Yu. T. Struchkov, V. Ts. Kampel, V. I. Bregadze, N. N. Godovikov, M. I. Kabachnik. Izv. Akad. Nauk SSSR, Ser. Khim.10, 2299 (1986).Search in Google Scholar

77d V. I. Bregadze, V. Ts. Kampel, E. I. Matrosov, V. A. Antonovich, A. I. Yanovskii, Yu. T. Struchkov, N. N. Godovikov, M. I. Kabachnik. Dokl. Akad. Nauk SSSR285, 1127 (1985).Search in Google Scholar

78 10.1021/ic2025846, A. V. Safronov, Y. V. Sevryugina, S. S. Jalisatgi, R. D. Kennedy, C. L. Barnes, M. F. Hawthorne. Inorg. Chem.51, 2629 (2012).Search in Google Scholar PubMed

79 10.1021/ic3014267, O. Bondarev, Y. V. Sevryugina, S. S. Jalisatgi, M. F. Hawthorne. Inorg. Chem.51, 9935 (2012).Search in Google Scholar PubMed

80 10.1021/om400097m, X. Zhang, X. Tang, J. Yang, Y. Li, H. Yan, V. I. Bregadze. Organometallics32, 2014 (2013).Search in Google Scholar

81 10.1002/ejic.201201518, K. Z. Kabytaev, T. A. Everett, A. V. Safronov, Y. V. Sevryugina, S. S. Jalisatgi, M. F. Hawthorne. Eur. J. Inorg. Chem. (2013). Online:Search in Google Scholar

82 10.1039/c2cs35441a, D. Olid, R. Núñez, C. Viñas, F. Teixidor. Chem. Soc. Rev.42, 3318 (2013).Search in Google Scholar PubMed

83 10.1002/anie.201209107, V. Lavallo, J. H. Wright, F. S. Tham, S. Quinlivan. Angew. Chem., Int. Ed.52, 3172 (2013).Search in Google Scholar PubMed

Online erschienen: 2013-4-29
Erschienen im Druck: 2013-4-30

© 2013 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 28.5.2023 from https://www.degruyter.com/document/doi/10.1351/PAC-CON-13-01-13/html
Scroll to top button