New ligand platforms featuring boron-rich clusters as organomimetic substituents

Alexander M. Spokoyny 1
  • 1 Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

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.

If the inline PDF is not rendering correctly, you can download the PDF file here.

  • 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).

  • 2

    , W. H. Brock, K. H. Jensen, C. K. Jørgensen. Polyhedron 2, 1 (1983).

    • Crossref
    • Export Citation
  • 3a

    W. N. Lipscomb. The Boranes and Their Relatives, Nobel Lecture, December 11, 1976.

  • 3b

    E. Muetterties. Boron Hydride Chemistry, Academic Press, New York (1975).

  • 4

    , M. Ephritikhine. Chem. Rev. 97, 2193 (1997).

  • 5

    , 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).

    • Crossref
    • Export Citation
  • 6

    , H. C. Brown, B. C. Rao. J. Org. Chem. 22, 1137 (1957).

  • 7

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

  • 8

    R. Grimes. Carboranes, 2nd ed., Elsevier (2011).

  • 9

    Original synthesis.

  • 9a

    , A. R. Pitochelli, M. F. Hawthorne. J. Am. Chem. Soc. 82, 3228 (1960); recently optimized process amenable to laboratory synthesis.

    • Crossref
    • Export Citation
  • 9b

    , V. Geis, K. Guttsche, H. Scherer, R. Uzun. Dalton Trans. 2687 (2009).

    • Crossref
    • Export Citation
  • 10

    R. N. Grimes. Metal Interactions with Boron Clusters, Plenum Press, New York (1982).

  • 11

    , 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).

    • Crossref
    • Export Citation
  • 12

    , M. Scholz, E. Hey-Hawkins. Chem. Rev. 111, 7035 (2011).

  • 13

    , B. P. Dash, R. Satapathy, J. A. Maguire, N. S. Hosmane. New J. Chem. 35, 1955 (2011).

    • Crossref
    • Export Citation
  • 14

    , F. Issa, M. Kassiou, L. M. Rendina. Chem. Rev. 111, 5701 (2011).

  • 15

    Review article (see references within):

  • 15a

    A. Kraft. Bull. Hist. Chem. 33, 61 (2008);

  • 15b

    , structural study (see references within): H. J. Buser, D. Schwarzenbach, W. Petter, A. Ludi. Inorg. Chem. 16, 2704 (1977).

    • Crossref
    • Export Citation
  • 16a

    E. Frankland. Experimental Researches in Pure, Applied and Physical Chemistry, John Van Voorst, London (1877).

  • 16b

    , D. Seyferth. Organometallics 20, 2940 (2001).

  • 17

    , D. F. Shriver. J. Am. Chem. Soc. 85, 3509 (1963).

  • 18

    , G. W. Parshall. J. Am. Chem. Soc. 86, 361 (1964).

  • 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.

  • 19b

    , J. R. Knorr, J. S. Merola. Organometallics 9, 3008 (1990).

  • 19c

    , 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).

    • Crossref
    • Export Citation
  • 20

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

  • 21

    , H. Braunschweig, R. D. Dewhurst, A. Schneider. Chem. Rev. 110, 3924 (2010).

    • Crossref
    • Export Citation
  • 22

    , H. Braunschweig, K. Radacki, A. Schneider. Science 328, 345 (2010).

    • Crossref
    • Export Citation
  • 23

    , J. A. Ibers, R. H. Holm. Science 209, 223 (1980).

  • 24a

    , M. M. Fein, J. E. Paustian, M. Sarakwash. Ind. Eng. Chem. Proc. Des. Dev. 5, 380 (1966).

    • Crossref
    • Export Citation
  • 24b

    , M. M. Fein, J. E. Paustian. Ind. Eng. Chem. Proc. Des. Dev. 4, 129 (1965).

    • Crossref
    • Export Citation
  • 24c

    , J. F. Ditter, E. B. Klusmann, J. D. Oakes, R. D. Williams. Inorg. Chem. 9, 889 (1970).

    • Crossref
    • Export Citation
  • 25

    , S. Papetti, C. Obenland, T. L. Heying. Ind. Eng. Chem. Prod. Res. Dev. 5, 334 (1966).

    • Crossref
    • Export Citation
  • 26a

    , K. Wade. J. Chem. Soc. D 792 (1971).

  • 26b

    D. M. P. Mingos. Nature 236, 99 (1972).

  • 26c

    , A. J. Welch. Chem. Commun. 49, 3615 (2013).

  • 27

    , 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).

    • Crossref
    • Export Citation
  • 28

    B–C bond formation:

  • 28a

    , L. I. Zakharkin, A. I. Kovredov, V. A. Olshevskaya, Z. S. Shaungumbekova. J. Organomet. Chem. 226, 217 (1982);

    • Crossref
    • Export Citation
  • 28b

    , B–O bond formation: K. Z. Kabytaev, S. N. Mukhin, I. V. Glukhov, Z. A. Starikova, V. I. Bregadze, I. P. Beletskaya. Organometallics 28, 4758 (2009);

    • Crossref
    • Export Citation
  • 28c

    , 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. Organometallics 27, 5937 (2008).

    • Crossref
    • Export Citation
  • 29

    , M. F. Hawthorne, D. C. Young, P. A. Wegner. J. Am. Chem. Soc. 87, 1818 (1965).

    • Crossref
    • Export Citation
  • 30

    , M. F. Hawthorne, G. B. Dunks. Science 178, 462 (1972).

  • 31

    , I. Rojo, F. Teixidor, C. Vi?as, R. Kivekäs, R. Sillanpää. Chem.—Eur. J. 9, 4311 (2003).

    • Crossref
    • Export Citation
  • 32a

    P. González-Cardoso, A. Stoica, P. Farràs, A. Pepiol, C. Viñas, F. Teixidor. Chem.—Eur. J. 16, 6660 (2010).

  • 32b

    , A. Pepiol, F. Teixidor, R. Sillanpää, M. Lupu, C. Viñas. Angew. Chem., Int. Ed. 50, 12491 (2011).

    • Crossref
    • Export Citation
  • 33

    , I. B. Sivaev, V. I. Bregadze. J. Organomet. Chem. 614–615, 27 (2000).

    • Crossref
    • Export Citation
  • 34

    , 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).

    • Crossref
    • Export Citation
  • 35

    , B. O’Regan, M. Grätzel. Nature 353, 737 (1991).

  • 36

    , T. W. Hamann, R. A. Jensen, A. B. F. Martinson, H. Van Ryswyk, J. T. Hupp. Energy Environ. Sci. 1, 66 (2008).

    • Crossref
    • Export Citation
  • 37

    , 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. C 115, 11257 (2011).

    • Crossref
    • Export Citation
  • 38

    , 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).

    • Crossref
    • Export Citation
  • 39

    , K. Tamao, Y. Kiso, K. Sumitani, M. Kumada. J. Am. Chem. Soc. 94, 9268 (1972).

    • Crossref
    • Export Citation
  • 40

    , G.-X. Jin. Coord. Chem. Rev. 248, 587 (2004).

  • 41

    , P. Dröse, C. G. Hrib, F. T. Edelmann. J. Am. Chem. Soc. 132, 15540 (2010).

    • Crossref
    • Export Citation
  • 42

    , D. Liu, L. Dang, Y. Sun, H.-S. Chan, Z. Lin, Z. Xie. J. Am. Chem. Soc. 130, 16103 (2008).

    • Crossref
    • Export Citation
  • 43

    , H. Shen, H.-S. Chan, Z. Xie. Organometallics 27, 5309 (2008).

  • 44

    , H. Wang, Y. Wang, H.-W. Li, Z. Xie. Organometallics 20, 5110 (2001).

    • Crossref
    • Export Citation
  • 45

    , X. Wang, G.-X. Jin. Organometallics 23, 6319 (2004).

  • 46

    , H. Heaney. Chem. Rev. 62, 81 (1962).

  • 47

    , J. D. Roberts, D. A. Semenow, H. E. Simmons Jr., L. A. Carlsmith. J. Am. Chem. Soc. 78, 601 (1956).

    • Crossref
    • Export Citation
  • 48

    , H. L. Gingrich, T. Ghosh, Q. Huang, M. Jones Jr. J. Am. Chem. Soc. 112, 4082 (1990).

    • Crossref
    • Export Citation
  • 49

    , L. Deng, H.-S. Chan, Z. Xie. J. Am. Chem. Soc. 128, 7728 (2006).

  • 50

    , Z. Qiu, S. Ren, Z. Xie. Acc. Chem. Res. 44, 299 (2011).

  • 51

    , 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).

    • Crossref
    • Export Citation
  • 52

    , J. R. Long, O. M. Yaghi. Chem. Soc. Rev. 38, 1213 (2009) and refs. Cited within.

    • Crossref
    • Export Citation
  • 53

    , O. K. Farha, J. T. Hupp. Acc. Chem. Res. 43, 1166 (2010).

  • 54

    , 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).

    • Crossref
    • Export Citation
  • 55

    , Y.-S. Bae, O. K. Farha, A. M. Spokoyny, C. A. Mirkin, J. T. Hupp, R. Q. Snurr. Chem. Commun. 4135 (2008).

    • Crossref
    • Export Citation
  • 56

    , O. K. Farha, A. M. Spokoyny, K. L. Mulfort, S. Galli, J. T. Hupp, C. A. Mirkin. Small 5, 1727 (2009).

    • Crossref
    • Export Citation
  • 57

    , Y.-S. Bae, A. M. Spokoyny, O. K. Farha, R. Q. Snurr, J. T. Hupp, C. A. Mirkin. Chem. Commun. 46, 3478 (2010).

    • Crossref
    • Export Citation
  • 58

    , S.-L. Huang, Y.-J. Lin, W.-B. Yu, G.-X. Jin. ChemPlusChem 77, 141 (2012).

    • Crossref
    • Export Citation
  • 59

    , S.-L. Huang, L.-H. Weng, G.-X. Jin. Dalton Trans. 41, 11657 (2012).

    • Crossref
    • Export Citation
  • 60

    , J. Müeller, K. Ba?e, T. F. Magnera, J. Michl. J. Am. Chem. Soc. 114, 9721 (1992).

    • Crossref
    • Export Citation
  • 61

    , A. M. Spokoyny, O. K. Farha, K. L. Mulfort, J. T. Hupp, C. A. Mirkin. Inorg. Chim. Acta 364, 266 (2010).

    • Crossref
    • Export Citation
  • 62a

    , E. L. Hoel, M. F. Hawthorne. J. Am. Chem. Soc. 97, 6388 (1975).

  • 62b

    , Z. Zheng, M. Diaz, C. B. Knobler, M. F. Hawthorne. J. Am. Chem. Soc. 117, 12338 (1995).

    • Crossref
    • Export Citation
  • 62c

    V. N. Kalinin, A. V. Usatov, L. I. Zakharkin. Proc. Indian Natl. Sci. Acad. 55, 293 (1989).

  • 63

    D. Morales-Morales, C. M. Jensen. The Chemistry of Pincer Compounds, Elsevier (2007).

  • 64

    , C. Gunanathan, L. J. W. Shimon, D. Milstein. J. Am. Chem. Soc. 131, 3146 (2009).

    • Crossref
    • Export Citation
  • 65

    , J. Zhao, A. S. Goldman, J. F. Hartwig. Science 307, 1080 (2005).

    • Crossref
    • Export Citation
  • 66

    , G. Lin, N. D. Jones, R. A. Gossage, R. McDonald, R. G. Cavell. Angew. Chem., Int. Ed. 42, 4054 (2003).

    • Crossref
    • Export Citation
  • 67

    , A. M. Spokoyny, M. G. Reuter, C. L. Stern, M. A. Ratner, T. Seidman, C. A. Mirkin. J. Am. Chem. Soc. 131, 9482 (2009).

    • Crossref
    • Export Citation
  • 68

    , J. I. Van der Vlugt. Angew Chem., Int. Ed. 49, 252 (2010).

  • 69

    , M. H. El-Zaria, H. Arii, H. Nakamura. Inorg. Chem. 50, 4149 (2011).

    • Crossref
    • Export Citation
  • 70

    , Y. Segawa, M. Yamashita, K. Nozaki. Science 314, 113 (2006).

    • Crossref
    • Export Citation
  • 71

    , Y. Segawa, M. Yamashita, K. Nozaki. J. Am. Chem. Soc. 131, 9201 (2009).

    • Crossref
    • Export Citation
  • 72

    , H. Ogawa, M. Yamashita. Dalton Trans. 45, 625 (2013).

  • 73

    , C. A. Tolman. Chem. Rev. 77, 313 (1977).

  • 74

    , 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).

    • Crossref
    • Export Citation
  • 75

    , J. Plešek, S. Heřmánek, B. Štíbr. J. Less Common Met. 67, 225 (1979).

    • Crossref
    • Export Citation
  • 76

    , F. Teixidor, G. Barberà, A. Vaca, R. Kivekäs, R. Sillanpää, J. Oliva, C. Viñas. J. Am. Chem. Soc. 127, 10158 (2005).

    • Crossref
    • Export Citation
  • 77a

    , A. M. Spokoyny, C. D. Lewis, G. Teverovskiy, S. L. Buchwald. Organometallics 31, 8478 (2012).

    • Crossref
    • Export Citation
  • 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).

  • 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).

  • 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 SSSR 285, 1127 (1985).

  • 78

    , A. V. Safronov, Y. V. Sevryugina, S. S. Jalisatgi, R. D. Kennedy, C. L. Barnes, M. F. Hawthorne. Inorg. Chem. 51, 2629 (2012).

    • Crossref
    • Export Citation
  • 79

    , O. Bondarev, Y. V. Sevryugina, S. S. Jalisatgi, M. F. Hawthorne. Inorg. Chem. 51, 9935 (2012).

    • Crossref
    • Export Citation
  • 80

    , X. Zhang, X. Tang, J. Yang, Y. Li, H. Yan, V. I. Bregadze. Organometallics 32, 2014 (2013).

    • Crossref
    • Export Citation
  • 81

    , K. Z. Kabytaev, T. A. Everett, A. V. Safronov, Y. V. Sevryugina, S. S. Jalisatgi, M. F. Hawthorne. Eur. J. Inorg. Chem. (2013). Online:

    • Crossref
    • Export Citation
  • 82

    , D. Olid, R. Núñez, C. Viñas, F. Teixidor. Chem. Soc. Rev. 42, 3318 (2013).

    • Crossref
    • Export Citation
  • 83

    , V. Lavallo, J. H. Wright, F. S. Tham, S. Quinlivan. Angew. Chem., Int. Ed. 52, 3172 (2013).

    • Crossref
    • Export Citation
FREE ACCESS

Journal + Issues

Pure and Applied Chemistry is the official monthly Journal of the International Union of Pure and Applied Chemistry (IUPAC), with responsibility for publishing works arising from those international scientific events and projects that are sponsored and undertaken by the Union.

Search