Abstract
The coordination chemistry of scorpionates, anionic tripodal boron-centered ligands that readily bind to virtually all main group, transition, and f-block metals, has had a profound effect in the development of synthetic bioinorganic chemistry during the past 50 years. Highlighted in this article are some of the most meaningful results published in the area, primarily in the preparation of structural and functional model compounds for the active sites in metalloproteins and metalloenzymes, a theme that encompasses topics as diverse as nitrogen fixation and heavy metal poisoning. It has also been 50 years since the genesis of Structure and Bonding, so let this account also be a celebration of the many contributions that the staunch serial has had on the entire field of inorganic chemistry during the past half century.
Keywords
The original version of this chapter was revised: Figure 10 of this chapter was displayed incorrect. The erratum to this chapter is available at DOI: 10.1007/430_2016_213.
An erratum to this chapter can be found at http://dx.doi.org/10.1007/430_2016_213
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsAbbreviations
- Ad:
-
Adamantyl
- ALAD:
-
5-Aminolevulinate dehydratase
- Bp:
-
Bis(pyrazolyl)borate
- But :
-
Tert-butyl
- CA:
-
Carbonic anhydrase
- Cp2Co:
-
Bis(cyclopentadienyl)cobalt (cobaltocene)
- Cys:
-
Cysteine
- DMSO:
-
Dimethyl sulfoxide
- Et:
-
Ethyl
- His:
-
Histidine
- HSAB:
-
Hard and soft acids and bases
- Im:
-
Imidazol-2-ylidene
- IR:
-
Infrared
- LADH:
-
Liver alcohol dehydrogenase
- Me:
-
Methyl
- Mes:
-
Mesityl (2,4,6-trimethylphenyl)
- MRI:
-
Magnetic resonance imaging
- NHC:
-
N-Heterocyclic carbene
- NHSe:
-
N-Heterocyclic selone
- NHT:
-
N-Heterocyclic thione
- Ph:
-
Phenyl
- Pri :
-
Isopropyl
- THF:
-
Tetrahydrofuran
- TmR :
-
Tris(mercaptoimidazolyl)borate
- ToR :
-
Tris(oxoimidazolyl)borate
- TpRR′ :
-
Tris(pyrazolyl)borate
- TseR :
-
Tris(selenoimidazolyl)borate
- TtR :
-
Tris(thioether)borate
- TtzRR′ :
-
Tris(triazolyl)borate
References
Hodgkin DC (1965) Science 150:979
Rosenberg B, Van Camp L, Krigas T (1965) Nature 205:698
Allen AD, Senoff CV (1965) Chem Commun 621
De Haën C (2001) Top Magn Reson Imaging 12:221
Caravan P, Ellison JJ, McMurry TJ, Lauffer RB (1999) Chem Rev 99:2293
Maiocchi A (2003) Mini Rev Med Chem 3:845
Schwochau K (1994) Angew Chem Int Ed Engl 33:2258
Liu S, Chakraborty S (2011) Dalton Trans 40:6077
Dessy R, Dillard J, Taylor L (eds) (1971) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970
Schrauzer GN (1971) Dessy R, Dillard J, Taylor L (eds) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970, Chap. 1, p 1
Allen AD (1971) Dessy R, Dillard J, Taylor L (eds) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970, Chap. 4, p 79
Wilkins RG (1971) Dessy R, Dillard J, Taylor L (eds) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970, p 111
Ulmer DD, Vallee BL (1971) Dessy R, Dillard J, Taylor L (eds) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970, Chap. 10, p 187
Gray HB (1971) Dessy R, Dillard J, Taylor L (eds) Bioinorganic chemistry, a symposium co-sponsored by the Division of Inorganic Chemistry of the American Chemical Society and the Chemical Institute of Canada at Virginia Polytechnic Institute and State University, Blacksburg, Va (Advances in chemistry series, No 100), June 22–25, 1970, Chap. 17, p 365
Rayner Canham GW, Lever ABP (1972) J Chem Educ 49:656
Williams DR (1971) The metals of life. Van Nostrand Reinhold, London
Williams DR (1976) An introduction to bio-inorganic chemistry. Charles C. Thomas, Springfield
Ochiai EI (1977) Bioinorganic chemistry: an introduction. Allen and Bacon, Boston
Holm RH (1977) Acc Chem Res 10:427
Hill HAO (1976) Chem Brit 12:119
Ibers JA, Holm RH (1980) Science 209:223
Karlin KD (1993) Science 261:701
Lee SC, Holm RH (2003) Proc Natl Acad Sci U S A 100:3595
Trofimenko S (1966) J Am Chem Soc 88:1842
Trofimenko S (1999) Scorpionates: the coordination chemistry of polypyrazolylborate ligands. Imperial College, London
Pettinari C (2008) Scorpionates II: chelating borate ligands. Imperial College, London
Santini C, Pellei M, Gioia Lobbia G, Papini G (2010) Mini Rev Org Chem 7:84
Sadimenko AP (2001) Adv Heterocycl Chem 81:167
Akita M, Hikichi S (2002) Bull Chem Soc Jpn 75:1657
Trofimenko S (2005) J Chem Educ 82:1715
Janiak C, Temizdemir S, Röhr C (2000) Z Anorg Allg Chem 626:1265
Dunne JF, Su J, Ellern A, Sadow AD (2008) Organometallics 27:2399
Papish ET, Dixon NA, Kumar M (2014) Struct Bond 160:115
Kernbach U, Ramm M, Luger P, Fehlhammer WP (1996) Angew Chem Int Ed Engl 35:310
Smith JM (2008) Comments Inorg Chem 29:189
Peters JC, Feldman JD, Tilley TD (1999) J Am Chem Soc 121:9871
Barney AA, Heyduk AD, Nocera DG (1999) Chem Commun 2379
Riordan CG (2010) Coord Chem Rev 254:1815
Parkin G (2007) New J Chem 31:1996
Spicer MD, Reglinski J (2009) Eur J Inorg Chem 1553
Reglinski J, Spicer MD (2015) Coord Chem Rev 297–298:181
Snyder CJ, Heeg MJ, Winter CH (2011) Inorg Chem 50:9210
Reger DL (1999) Comments Inorg Chem 21:1
Pettinari C, Pettinari R (2005) Coord Chem Rev 249:525
Bigmore HR, Lawrence SC, Mountford P, Tredget CS (2005) Dalton Trans 635
Pullen EE, Rabinovich D, Incarvito CD, Concolino TE, Rheingold AL (2000) Inorg Chem 39:1561
Holmes C, Carrano CJ (1991) Inorg Chem 30:1231
Butler A, Baldwin AH (1997) Struct Bond 89:109
Rajagopalan KV (1988) Annu Rev Nutr 8:401
McMaster J, Enemark JH (1998) Curr Opin Chem Biol 2:201
Feng C, Tollin G, Enemark JH (2007) Biochim Biophys Acta 1774:527
Enemark JH, Cooney JJA, Wang JJ, Holm RH (2004) Chem Rev 104:1175
Romão MJ, Huber R (2004) Chem Rev 104:1175
Romão MJ, Huber R (1998) Struct Bond 90:69
Hagen WR, Arendsen AF (1998) Struct Bond 90:161
Bevers LE, Hagedoorn PL, Hagen WR (2009) Coord Chem Rev 253:269
Thomas S, Tiekink ERT, Young CG (1996) Organometallics 15:2428
Eagle AA, Harben SM, Tiekink ERT, Young CG (1994) J Am Chem Soc 116:9749
Wieghardt K (1989) Angew Chem Int Ed Engl 28:1153
Yocum CF, Pecoraro VL (1999) Curr Opin Chem Biol 3:182
Miriyala S, Spasojevic I, Tovmasyan A, Salvemini D, Vujaskovic Z, St Clair D, Batinic-Haberle I (2012) Biochim Biophys Acta 1822:794
Kitajima N, Osawa M, Tamura N, Moro-oka Y, Hirano T, Hirobe M, Nagano T (1993) Inorg Chem 32:1879
Singh UP, Sharma AK, Hikichi S, Komatsuzaki H, Moro-oka Y, Akita M (2006) Inorg Chim Acta 359:4407
Armstrong WH, Spool A, Papaefthymiou GC, Frankel RB, Lippard SJ (1984) J Am Chem Soc 106:3653
Feig AL, Lippard SJ (1994) Chem Rev 94:759
Stenkamp RE (1994) Chem Rev 94:715
Ogihara T, Hikichi S, Akita M, Moro-oka Y (1998) Inorg Chem 37:2614
Ryle MJ, Hausinger RP (2002) Curr Opin Chem Biol 6:193
Bugg TDH, Ramaswamy S (2008) Curr Opin Chem Biol 12:134
Abu-Omar MM, Loaiza A, Hontzeas N (2005) Chem Rev 105:2227
Kovaleva EG, Lipscomb JD (2008) Nat Chem Biol 4:187
Oloo WN, Que L Jr (2015) Acc Chem Res 48:2612
Sallmann M, Limberg C (2015) Acc Chem Res 48:2734
Paine TK, Que L Jr (2014) Struct Bond 160:39
Gennari M, Marchiò L (2009) Curr Bioact Compd 5:244
Kitajima N, Tolman WB (1995) Prog Inorg Chem 43:419
Kitajima N, Moro-oka Y (1994) Chem Rev 94:737
Blackman AG, Tolman WB (2000) Struct Bond 97:179
Kitajima N, Fujisawa K, Fujimoto C, Moro-oka Y, Hashimoto S, Kitagawa T, Toriumi K, Tatsumi K, Nakamura A (1992) J Am Chem Soc 114:1277
Trofimenko S, Calabrese JC, Thompson JS (1987) Inorg Chem 26:1507
Ruggiero CE, Carrier SM, Antholine WE, Whittaker JW, Cramer CJ, Tolman WB (1993) J Am Chem Soc 115:11285
Enemark JH, Feltham RD (1974) Coord Chem Rev 13:339
Suzuki S, Kataoka K, Yamaguchi K, Inoue T, Kai Y (1999) Coord Chem Rev 190–192:245
Merkle AC, Lehnert N (2012) Dalton Trans 41:3355
Kimura E, Koike T, Shionoya M (1997) Struct Bond 89:1
Vahrenkamp H (1999) Acc Chem Res 32:589
Parkin G (2000) Chem Commun 1971
Parkin G (2004) Chem Rev 104:699
Keilin D, Mann T (1940) Biochem J 34:1163
Alsfasser R, Trofimenko S, Looney A, Parkin G, Vahrenkamp H (1991) Inorg Chem 30:4098
Looney A, Han R, McNeill K, Parkin G (1993) J Am Chem Soc 115:4690
Trofimenko S (1967) J Am Chem Soc 89:3170
Janiak C, Scharmann TG, Green JC, Parkin RPG, Kolm MJ, Riedel E, Mickler W, Elguero J, Claramunt RM, Sanz D (1996) Chem Eur J 2:992
Janiak C, Scharmann TG, Günther W, Hinrichs W, Lentz D (1996) Chem Ber 129:991
Santini C, Pellei M, Gioia Lobbia G, Fedeli D, Falcioni G (2003) J Inorg Biochem 94:348
Kumar M, Dixon NA, Merkle AC, Zeller M, Lehnert N, Papish ET (2012) Inorg Chem 51:7004
Fränkel R, Kernbach U, Bakola-Christianopoulou M, Plaia U, Suter M, Ponikwar W, Nöth H, Moinet C, Fehlhammer WP (2001) J Organomet Chem 617–618:530
Nieto I, Cervantes-Lee F, Smith JM (2005) Chem Commun 3811
Hahn FE, Jahnke MC (2008) Angew Chem Int Ed 47:3122
Hopkinson MN, Richter C, Schedler M, Glorius F (2014) Nature 510:485
Díez-González S, Nolan SP (2007) Coord Chem Rev 251:874
Smith JM (2014) Prog Inorg Chem 58:417
Scepaniak JJ, Young JA, Bontchev RP, Smith JM (2009) Angew Chem Int Ed 48:3158
Scepaniak JJ, Vogel CS, Khusniyarov MM, Heinemann FW, Meyer K, Smith JM (2011) Science 331:1049
Ge P, Haggerty BS, Rheingold AL, Riordan CG (1994) J Am Chem Soc 116:8406
Ohrenberg C, Ge P, Schebler P, Riordan CG, Yap GPA, Rheingold AL (1996) Inorg Chem 35:749
Pearson RG (1963) J Am Chem Soc 85:3533
Ohrenberg C, Saleem MM, Riordan CG, Yap GPA, Verma AK, Rheingold AL (1996) Chem Commun 1081
Schebler P, Mandimutsira BS, Riordan CG, Liable-Sands LM, Incarvito CD, Rheingold AL (2001) J Am Chem Soc 123:331
Fujita K, Rheingold AL, Riordan CG (2003) Dalton Trans 2004
Chiou SJ, Innocent J, Riordan CG, Lam KC, Liable-Sands L, Rheingold AL (2000) Inorg Chem 39:4347
Penner-Hahn J (2007) Curr Opin Chem Biol 11:166
Matthews RG (2001) Acc Chem Res 34:681
Krishnan R, Voo JK, Riordan CG, Zahkarov L, Rheingold AL (2003) J Am Chem Soc 125:4422
Mandimutsira BS, Yamarik JL, Brunold TC, Gu W, Cramer SP, Riordan CG (2001) J Am Chem Soc 123:9194
Barney AA, Heyduk AF, Nocera DG (1999) Chem Commun 2379
Mehn MP, Peters JC (2006) J Inorg Biochem 100:634
Betley TA, Peters JC (2004) J Am Chem Soc 126:6252
Hendrich MP, Gunderson W, Behan RK, Green MT, Mehn MP, Betley TA, Lu CC, Peters JC (2006) Proc Natl Acad Sci U S A 103:17107
Garner M, Reglinski J, Cassidy I, Spicer MD, Kennedy AR (1996) Chem Commun 1975
Raper ES (1985) Coord Chem Rev 61:115
Akrivos PD (2001) Coord Chem Rev 213:181
Reglinski J, Spicer MD (2009) Curr Bioact Compd 5:264
Bridgewater BM, Parkin G (2001) Inorg Chem Commun 4:126
Tran BL, Carrano CJ (2007) Inorg Chem 46:5429
Wallace D, Gibson LT, Reglinski J, Spicer MD (2007) Inorg Chem 46:3804
Bridgewater BM, Parkin G (2000) J Am Chem Soc 122:7140
Magyar JS, Weng TC, Stern CM, Dye DF, Rous BW, Payne JC, Bridgewater BM, Mijovilovich A, Parkin G, Zaleski JM, Penner-Hahn JE, Godwin HA (2005) J Am Chem Soc 127:9495
Rabinovich D (2006) Struct Bond 120:143
Bridgewater BM, Fillebeen T, Friesner RA, Parkin G (2000) J Chem Soc Dalton Trans 4494
Auld DS (2001) BioMetals 14:271
Lipscomb WN, Sträter N (1996) Chem Rev 96:2375
Hightower KE, Fierke CA (1999) Curr Opin Chem Biol 3:176
Sedgwick B, Lindahl T (2002) Oncogene 21:8886
Lindahl T, Sedgwick B, Sekiguchi M, Nakabeppu Y (1988) Annu Rev Plant Physiol Plant Mol Biol 57:133
Wilker JJ, Lippard SJ (1995) J Am Chem Soc 117:8682
Wilker JJ, Lippard SJ (1997) Inorg Chem 36:969
Grapperhaus CA, Tuntulani T, Reibenspies JH, Darensbourg MY (1998) Inorg Chem 37:4052
Brand U, Rombach M, Vahrenkamp H (1998) Chem Commun 2717
Rombach M, Vahrenkamp H (2001) Inorg Chem 40:6144
Brand U, Rombach M, Seebacher J, Vahrenkamp H (2001) Inorg Chem 40:6151
Seebacher J, Ji M, Vahrenkamp H (2004) Eur J Inorg Chem 409
Ji M, Vahrenkamp H (2005) Eur J Inorg Chem 1398
Ji M, Benkmil B, Vahrenkamp H (2005) Inorg Chem 44:3518
Ibrahim MM, He G, Seebacher J, Benkmil B, Vahrenkamp H (2005) Eur J Inorg Chem 4070
Ibrahim MM, Seebacher J, Steinfeld G, Vahrenkamp H (2005) Inorg Chem 44:8531
Docrat A, Morlok MM, Bridgewater BM, Churchill DG, Parkin G (2004) Polyhedron 23:481
Morlok MM, Janak KE, Zhu G, Quarless DA, Parkin G (2006) J Inorg Biochem 100:1147
Melnick JG, Zhu G, Buccella D, Parkin G (2005) J Am Chem Soc 127:14039
Chiou SJ, Riordan CG, Rheingold AL (2003) Proc Natl Acad Sci U S A 100:3695
Warthen CR, Hammes BS, Carrano CJ, Crans DC (2001) J Biol Inorg Chem 6:82
Hammes BS, Carrano CJ (2001) Inorg Chem 40:919
Smith JN, Shirin Z, Carrano CJ (2003) J Am Chem Soc 125:868
Smith JN, Hoffman JT, Shirin Z, Carrano CJ (2005) Inorg Chem 44:2012
Notni J, Görls H, Anders E (2006) Eur J Inorg Chem 1444
Notni J, Günther W, Anders E (2007) Eur J Inorg Chem 985
Ibrahim MM (2010) J Sulfur Chem 31:395
Ibrahim MM, Mosa A (2014) Arab J Chem 7:672
Picot D, Ohanessian G, Frison G (2008) Inorg Chem 47:8167
Isaac M, Latour JM, Sénèque O (2012) Chem Sci 3:3409
Melnick JG, Parkin G (2007) Science 317:225
Al-Harbi A, Sattler W, Sattler A, Parkin G (2011) Chem Commun 47:3123
Minoura M, Landry VK, Melnick JG, Pang K, Marchiò L, Parkin G (2006) Chem Commun 3990
Landry VK, Pang K, Quan SM, Parkin G (2007) Dalton Trans 820
Landry VK, Buccella D, Pang K, Parkin G (2007) Dalton Trans 866
Bailey PJ, Lanfranchi M, Marchiò L, Parsons S (2001) Inorg Chem 40:5030
Cammi R, Gennari M, Giannetto M, Lanfranchi M, Marchiò L, Mori G, Paiola C, Pellinghelli MA (2005) Inorg Chem 44:4333
Silva RM, Gwengo C, Lindeman SV, Smith MD, Gardinier JR (2006) Inorg Chem 45:10998
Silva RM, Gwengo C, Lindeman SV, Smith MD, Long GJ, Grandjean F, Gardinier JR (2008) Inorg Chem 47:7239
Imran M, Neumann B, Stammler HG, Monkowius U, Ertl M, Mitzel NW (2013) Dalton Trans 42:15785
Imran M, Mix A, Neumann B, Stammler HG, Monkowius U, Bleckenwegner P, Mitzel NW (2014) Dalton Trans 43:10956
Imran M, Mix A, Neumann B, Stammler HG, Monkowius U, Bleckenwegner P, Mitzel NW (2014) Dalton Trans 43:14737
Acknowledgments
Insightful discussions with Professors Joshua Telser (Roosevelt University), Brian Hoffman (Northwestern University), and Bill Jensen (University of Cincinnati) regarding the first public use of the term “bioinorganic” are sincerely appreciated. The National Science Foundation (Award No. CHE-0911407) and The University of North Carolina at Charlotte are gratefully acknowledged for support of our research in synthetic bioinorganic chemistry since 1996.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Rabinovich, D. (2016). Synthetic Bioinorganic Chemistry: Scorpionates Turn 50. In: Mingos, D. (eds) 50 Years of Structure and Bonding – The Anniversary Volume. Structure and Bonding, vol 172. Springer, Cham. https://doi.org/10.1007/430_2015_212
Download citation
DOI: https://doi.org/10.1007/430_2015_212
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-35136-0
Online ISBN: 978-3-319-35138-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)