Hydrated metal ions in aqueous solution: How regular are their structures?

Ingmar Persson 1
  • 1 Department of Chemistry, Swedish University of Agricultural Sciences, P.O. Box 7015, SE-750 07 Uppsala, Sweden

The hydration reaction is defined as the transfer of an ion or neutral chemical species from the gaseous phase into water, Mn+(g) → Mn+(aq). In this process, water molecules bind to metal ions through ion-dipole bonds of mainly electrostatic character. The hydration reaction is always strongly exothermic with increasing heat of hydration with increasing charge density of the ion. The structures of the hydrated metal ions in aqueous solution display a variety of configurations depending on the size and electronic properties of the metal ion. The basic configurations of hydrated metal ions in aqueous solution are tetrahedral, octahedral, square antiprismatic, and tricapped trigonal prismatic. This paper gives an overview of the structures of hydrated metal ions in aqueous solution with special emphasis on those with a non-regular coordination figure. Metal ions without d-electrons in the valance shell form regular aqua complexes with a coordination figure, allowing a maximum number of water molecules to be clustered around the metal ion. This number is dependent on the ratio of the metal ion radius to the atomic radius of oxygen in a coordinated water molecule (1.34 Å). The lighter lanthanoid(III) ions have a regular tricapped trigonal prismatic configuration with the M–O distance to the capping water molecules somewhat longer than to the prismatic ones. However, with increasing atomic number of the lanthanoid(III) ions, an increasing distortion of the capping water molecules is observed, resulting in a partial loss of water molecules in the capping positions for the heaviest lanthanoids. Metal ions with d4 and d9 valance shell electron configuration, as chromium(II) and copper(II), respectively, have Jahn–Teller distorted aqua complexes. Metal ions with low charge and ability to form strong covalent bonds, as silver(I), mercury(II), palladium(II), and platinum(II), often display distorted coordination figures due to the second-order Jahn–Teller effect. Metal ions with d10s2 valence shell electron configuration may have a stereochemically active lone electron pair (hemi-directed complexes) or an inactive one (holo-directed). The hydrated tin(II), lead(II), and thallium(I) ions are hemi-directed in aqueous solution, while the hydrated bismuth(III) ion is holo-directed. The structures of the hydrated cationic oxo-metal ions are reported as well.

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  • 1

    , D. R. Rosseinsky. Chem. Rev. 65, 467 (1965).

  • 2

    C. G. Phillips, R. J. P. Williams. Inorganic Chemistry, Vol. 1, p. 161, Clarendon Press, New York (1965).

  • 3

    , R. G. Pearson. J. Am. Chem. Soc. 85, 3533 (1963).

  • 4

    , J. K. Beattie, S. P. Best, B. W. Skelton, A. H. White. J. Chem. Soc., Dalton Trans. 2105 (1981).

    • Crossref
    • Export Citation
  • 5

    , D. Lundberg, I. Persson, L. Eriksson, P. D’Angelo, S. De Panfilis. Inorg. Chem. 49, 4420 (2010).

    • Crossref
    • Export Citation
  • 6

    , R. Ireland, P. Wipf, J. Armstrong. J. Org. Chem. 56, 650 (1991).

    • Crossref
    • Export Citation
  • 7

    , J. Näslund, I. Persson, M. Sandström. Inorg. Chem. 39, 4012 (2000).

    • Crossref
    • Export Citation
  • 8

    Inorganic Crystal Structure Database 1.4.6, Release 2009-1, FIZ Karlsruhe (2009).

  • 9a

    , F. H. Allen. Acta Crystallogr., Sect. B 58, 380 (2002).

  • 9b

    Cambridge Structure Database, Release 2008.

  • 10

    , H. Ohtaki, T. Radnai. Chem. Rev. 93, 1157 (1993) and refs. therein.

    • Crossref
    • Export Citation
  • 11

    , G. Johansson. Adv. Inorg. Chem. 39, 159 (1992) and refs. therein.

    • Crossref
    • Export Citation
  • 12

    I. Persson. Unpublished data.

  • 13

    , P. D’Angelo, I. Persson. Inorg. Chem. 43, 3543 (2004).

  • 14

    T. Yamaguchi, H. Ohtaki, E. Spohr, G. Palinkas, K. Heinzinger, M. Probst. Z. Naturforsch., A 41, 1175 (1986).

  • 15

    , F. Jalilehvand, D. Spångberg, P. Lindqvist-Reis, K. Hermansson, I. Persson, M. Sandström. J. Am. Chem. Soc. 123, 431 (2001).

    • Crossref
    • Export Citation
  • 16

    I. Persson, M. Sandström, H. Yokoyama, M. Chaudhry. Z. Naturforsch., A 50, 21 (1995).

  • 17

    , A. Abbasi, P. Lindqvist-Reis, L. Eriksson, D. Sandström, S. Lidin, I. Persson, M. Sandström. Chem.—Eur. J. 11, 4065 (2005).

    • Crossref
    • Export Citation
  • 18

    , P. Lindqvist-Reis, I. Persson, M. Sandström. Dalton Trans. 3868 (2006).

    • Crossref
    • Export Citation
  • 19

    , P. Lindqvist-Reis, K. Lamble, S. Pattanaik, M. Sandström, I. Persson. J. Phys. Chem. B 104, 402 (2000).

    • Crossref
    • Export Citation
  • 20

    , J. Näslund, P. Lindqvist-Reis, S. Pattanaik, M. Sandström, I. Persson. Inorg. Chem. 39, 4006 (2000).

    • Crossref
    • Export Citation
  • 21

    , H. Tachikawa, T. Ichikawa, H. Yoshida. J. Am. Chem. Soc. 112, 977 (1990).

    • Crossref
    • Export Citation
  • 22

    , C. Hagfeldt, V. Kessler, I. Persson. Dalton Trans. 2142 (2004).

  • 23

    , H. Loeffler, J. Iglesias Yagüe, B. M. Rode. Chem. Phys. Lett. 363, 367 (2002).

    • Crossref
    • Export Citation
  • 24

    , T. Miyanaga, I. Watanabe, S. Ikeda. Chem. Lett. 1073 (1988).

  • 25

    , S. P. Cramer, P. K. Eidem, M. T. Pafett, J. R. Winkler, Z. Dori, H. B. Gray. J. Am. Chem. Soc. 105, 799 (1983).

    • Crossref
    • Export Citation
  • 26

    , P. Lindqvist-Reis, S. Diaz-Moreno, A. Munoz-Páez, S. Pattanaik, I. Persson, M. Sandström. Inorg. Chem. 37, 6675 (1998), and refs. therein.

    • Crossref
    • Export Citation
  • 27

    , M. Brorson, M. Gajhede. Inorg. Chem. 26, 2109 (1987).

  • 28

    , D. Lundberg, A.-S. Ullström, P. D’Angelo, I. Persson. Inorg. Chim. Acta 360, 1809 (2007).

    • Crossref
    • Export Citation
  • 29

    M. Taimisto, R. Oilunkaniemi, R. S. Laitinen, M. Ahlgren. Z. Naturforsch., B 58, 959 (2003).

  • 30

    , S. P. Best, J. Bruce Forsyth. J. Chem. Soc., Dalton Trans. 3507 (1990).

    • Crossref
    • Export Citation
  • 31

    , P. Bernhard, H.-B. Bürgi, J. Hauser, H. Lehmann, A. Ludi. Inorg. Chem. 21, 3936 (1982).

    • Crossref
    • Export Citation
  • 32

    , R. Caminiti, D. Atzei, P. Cucca, A. Anedda, G. Bongiovanni. J. Phys. Chem. 90, 238 (1986).

    • Crossref
    • Export Citation
  • 33

    , M. C. Read, M. Sandström. Acta Chem. Scand. 46, 1177 (1992).

    • Crossref
    • Export Citation
  • 34

    , R. S. Armstrong, J. K. Beattie, S. P. Best, B. W. Skelton, A. H. White. J. Chem. Soc., Dalton Trans. 1973 (1983).

    • Crossref
    • Export Citation
  • 35

    , O. Kristiansson, I. Persson, D. Bobicz, D. Xu. Inorg. Chim Acta 344, 15 (2003).

    • Crossref
    • Export Citation
  • 36

    , T. S. Hofer, B. R. Randolf, A. Ali Shah, B. M. Rode, I. Persson. Chem. Phys Lett. 445, 193 (2007).

    • Crossref
    • Export Citation
  • 37

    , E. C. Beret, R. R. Pappalardo, N. L. Doltsinis, D. Marx, E. S. Marcos. ChemPhysChem 9, 237 (2008).

    • Crossref
    • Export Citation
  • 38

    J. Purans, B. Fourest, C. Cannes, V. Sladkov, F. David, L. Venault, M. Lecomte. J. Chem. Phys. B 109, 11074 (2005).

  • 39

    , F. Jalilehvand, L. J. Laffin. Inorg. Chem. 47, 3248 (2008).

  • 40

    , T. S. Hofer, B. R. Randolf, B. M. Rode, I. Persson. Dalton Trans. 1512 (2009).

    • Crossref
    • Export Citation
  • 41

    , I. Persson, J. E. Penner-Hahn, K. O. Hodgson. Inorg. Chem. 32, 2497 (1993).

    • Crossref
    • Export Citation
  • 42

    , I. Persson, P. Persson, M. Sandström, A.-S. Ullström. J. Chem. Soc., Dalton Trans. 1256 (2002) and refs. therein.

    • Crossref
    • Export Citation
  • 43

    , J. Chaboy, A. Munoz-Paez, P. J. Merkling, E. S. Marcos. J. Chem. Phys. 124, 064509 (2006).

    • Crossref
    • Export Citation
  • 44

    , V. S. Bryantsev, M. S. Diallo, A. C. T. van Duin, W. A. Goddard III. J. Phys. Chem. A 112, 9104 (2008).

    • Crossref
    • Export Citation
  • 45

    , I. Persson, K. B. Nilsson. Inorg. Chem. 45, 7428 (2006).

  • 46

    , I. Persson, L. Eriksson, P. Lindqvist-Reis, P. Persson, M. Sandström. Chem.—Eur. J. 14, 6687 (2008).

    • Crossref
    • Export Citation
  • 47

    , J. Glaser, G. Johansson. Acta Chem. Scand., Ser. A 36a, 125 (1982).

    • Crossref
    • Export Citation
  • 48

    , J. Blixt, J. Glaser, J. Mink, I. Persson, P. Persson, M. Sandström. J. Am. Chem. Soc. 117, 5089 (1995).

    • Crossref
    • Export Citation
  • 49

    , I. Persson, F. Jalilehvand, M. Sandström. Inorg. Chem. 41, 192 (2002).

    • Crossref
    • Export Citation
  • 50

    , I. Persson, P. D’Angelo, S. De Panfilis, M. Sandström, L. Eriksson. Chem.—Eur. J. 14, 3056 (2008) and refs. therein.

    • Crossref
    • Export Citation
  • 51

    P. D’Angelo, A. Zitalo, V. Migliorati, G. Mancini, I. Persson, G. Chillemi. Chem.—Eur. J. 16 682 (2010).

  • 52

    , P. G. Allen, J. J. Bucher, D. K. Shuh, N. M. Edelstein, I. Craig. Inorg. Chem. 39, 595 (2000).

    • Crossref
    • Export Citation
  • 53

    , J. H. Matonic, B. L. Scott, M. P. Neu. Inorg. Chem. 40, 2638 (2001).

    • Crossref
    • Export Citation
  • 54

    , P. Lindqvist-Reis, C. Apostolidis, J. Rebizant, A. Morgenstern, R. Klenze, O. Walter, T. Fanghaenel, R. G. Haire. Angew. Chem., Int. Ed. 46, 919 (2007).

    • Crossref
    • Export Citation
  • 55

    , S. Skanthakumar, M. R. Antonio, R. E. Wilson, L. Soderholm. Inorg. Chem. 46, 3485 (2007).

    • Crossref
    • Export Citation
  • 56

    , N. Torapava, I. Persson, L. Eriksson, D. Lundberg. Inorg. Chem. 48, 11712 (2009).

    • Crossref
    • Export Citation
  • 57

    , H. Moll, M. A. Denecke, F. Jalilehvand, M. Sandström, I. Grenthe. Inorg. Chem. 38, 1795 (1999).

    • Crossref
    • Export Citation
  • 58

    , A. Ikeda-Ohno, C. Hennig, A. Rossberg, H. Fune, A. C. Scheinost, G. Bernhard, T. Yaita. Inorg. Chem. 47, 8294 (2008).

    • Crossref
    • Export Citation
  • 59

    , P. G. Allen, J. J. Bucher, D. K. Shuh, N. M. Edelstein, T. Reich. Inorg. Chem. 36, 4676 (1997).

    • Crossref
    • Export Citation
  • 60

    , S. D. Conradson, K. D. Abney, B. D. Begg, E. D. Brady, D. L. Clark, C. den Auwer, M. Ding, P. K. Dorhout, F. J. Espinosa-Faller, P. L. Gordon, R. G. Haire, N. J. Hess, R. F. Hess, D. W. Keogh, G. H. Lander, A. J. Lupinetti, L. A. Morales, M. P. Neu, P. D. Palmer, P. Paviet-Hartmann, S. D. Reilly, W. H. Runde, C. D. Tait, D. K. Veirs, F. Wastin. Inorg. Chem. 43, 116 (2004).

    • Crossref
    • Export Citation
  • 61

    S. D. Conradson, D. L. Clark, M. P. Neu, W. H. Runde, C. D. Tait. Los Alamos Sci. 26, 418 (2000).

  • 62

    , M. Åberg, D. Ferri, J. Glaser, I. Grenthe. Inorg. Chem. 22, 3986 (1983).

    • Crossref
    • Export Citation
  • 63a

    , R. D. Shannon. Acta Crystallogr., Sect. A 32, 751 (1976).

  • 63b

    , R. D. Shannon, C. T. Prewitt. Acta Crystallogr., Sect. B 25, 925 (1969).

    • Crossref
    • Export Citation
  • 64

    , G. Moreau, L. Helm, J. Purans, A. E. Merbach. J. Phys. Chem. A 106, 3034 (2002).

    • Crossref
    • Export Citation
  • 65

    , J. Sygusch. Acta Crystallogr., Sect. B 30, 662 (1974).

  • 66

    , M. A. S. Aquino, W. Clegg, Q.-T. Liu, A. G. Sykes. Acta Crystallogr., Sect. C 51, 560 (1995).

    • Crossref
    • Export Citation
  • 67

    , J. Rosdahl, I. Persson, L. Kloo, K. Ståhl. Inorg. Chim. Acta 357, 2624 (2004).

    • Crossref
    • Export Citation
  • 68

    I. B. Bersuker. Electronic Structure and Properties of Transition Metal Compounds, Chaps. 7.3 and 9.4, Wiley-Interscience, New York (1996).

  • 69

    , F. Bramsen, A. D. Bond, C. J. McKenzie. Acta Crystallogr., Sect. E 59, i105 (2003).

    • Crossref
    • Export Citation
  • 70

    , R. Song, K. M. Kim, Y. S. Sohn. Inorg. Chim. Acta 304, 156 (2000).

    • Crossref
    • Export Citation
  • 71

    , T. C. W. Mak, C. H. L. Kennard, G. Smith, E. J. O’Reilly, D. S. Sagatys, J. C. Fulwood. Polyhedron 6, 855 (1987).

    • Crossref
    • Export Citation
  • 72

    , C. Yue, Z. Lin, L. Chen, F. Jiang, M. Hong. J. Mol. Struct. 779, 16 (2005).

    • Crossref
    • Export Citation
  • 73

    , Y. Kajikawa, N. Azuma, K. Tajima. Inorg. Chim. Acta 288, 90 (1999).

    • Crossref
    • Export Citation
  • 74

    , O. Guillou, P. Bergerat, O. Kahn, E. Bakalbassis, K. Boubekeur, P. Batail, M. Guillot. Inorg. Chem. 31, 110 (1992).

    • Crossref
    • Export Citation
  • 75

    , V. Shivaiah, S. K. Das. Angew. Chem., Int. Ed. 45, 245 (2006).

    • Crossref
    • Export Citation
  • 76

    , T. C. W. Mak, C. H. L. Kennard, G. Smith, E. J. O’Reilly, D. S. Sagatys, J. C. Fulwood. Polyhedron 6, 855 (1987).

    • Crossref
    • Export Citation
  • 77

    , A. Pasquarello, I. Petri, P. S. Salmon, O. Parisel, R. Car, E. Toth, D. H. Powell, H. F. Fischer, L. Helm, A. E. Merbach. Science 291, 856 (2001).

    • Crossref
    • Export Citation
  • 78

    , M. Benfatto, P. D’Angelo, S. D. Longa, N. V. Pavel. Phys. Rev. B 65, 174205 (2002).

    • Crossref
    • Export Citation
  • 79

    , P. Frank, M. Benfatto, R. K. Szilagyi, P. D’Angelo, S. D. Longa, K. O. Hodgson. Inorg. Chem. 44, 1922 (2005).

    • Crossref
    • Export Citation
  • 80

    , S. Ray, A. Zalkin, D. H. Templeton. Acta Crystallogr., Sect. B 29, 2748 (1973).

    • Crossref
    • Export Citation
  • 81

    , A. C. Blackburn, J. C. Gallucci, R. E. Gerkin. Acta Crystallogr., Sect. C 47, 2019 (1991).

    • Crossref
    • Export Citation
  • 82

    , F. A. Cotton, L. R. Falvello, C. A. Murillo, J. F. Quesada. J. Solid State Chem. 96, 192 (1992).

    • Crossref
    • Export Citation
  • 83

    , M. A. Araya, F. A. Cotton, L. M. Daniels, L. R. Favello, C. A. Murillo. Inorg. Chem. 32, 4853 (1993).

    • Crossref
    • Export Citation
  • 84

    , B. N. Figgis, E. S. Kucharski, P. A. Reynolds. Acta Crystallogr., Sect. B 46, 577 (1990).

    • Crossref
    • Export Citation
  • 85

    , G. Johansson, M. Sandström. Acta Chem. Scand., Ser. A 32a, 109 (1978).

    • Crossref
    • Export Citation
  • 86

    , A. Molla-Abbassi, L. Eriksson, P. Lindqvist-Reis, J. Mink, I. Persson, M. Sandström, M. Skripkin, A.-S. Ullström. J. Chem. Soc., Dalton Trans. 4357 (2002).

    • Crossref
    • Export Citation
  • 87

    , L. E. Orgel. J. Chem. Soc. 4186 (1958).

  • 88

    R. S. Nyholm. J. Chem. Soc., Proc. 273 (1961).

  • 89

    I. B. Bersuker. The Jahn–Teller Effect and Vibronic Interactions in Modern Chemistry, Chaps. 1–5, Plenum, New York (1984).

  • 90

    I. B. Bersuker, V. Z. Polinger. Vibronic Interactions in Molecules and Crystals, Chaps. 3 and 4, Springer-Verlag, Berlin (1989).

  • 91

    , D. Strömberg, M. Sandström, U. Wahlgren. Chem. Phys. Lett. 172, 49 (1990).

    • Crossref
    • Export Citation
  • 92

    , G. Meyer, P. Nockemann. Z. Anorg. Allg. Chem. 629, 1447 (2003).

    • Crossref
    • Export Citation
  • 93

    , T. Yamaguchi, G. Johansson, B. Holmberg, M. Maeda, H. Ohtaki. Acta Chem. Scand., Ser A 38a, 437 (1984).

    • Crossref
    • Export Citation
  • 94

    , M. Maeda, Y. Maegawa, T. Yamaguchi, H. Wakita. Bull. Chem. Soc. Jpn. 52, 2545 (1979).

    • Crossref
    • Export Citation
  • 95

    , M. Sandström, G. W. Neilson, G. Johansson, T. Yamaguchi. J. Phys. C, Solid State Phys. 18, L1115 (1985).

    • Crossref
    • Export Citation
  • 96

    , T. Yamaguchi, O. Lindqvist, J. B. Boyce, T. Claesson. Acta Chem. Scand., Ser A 38a, 423 (1984).

    • Crossref
    • Export Citation
  • 97

    , T. M. Seward, C. M. B. Henderson, J. M. Charnock, B. R. Dobson. Geochim. Cosmochim. Acta 60, 2273 (1996).

    • Crossref
    • Export Citation
  • 98

    S. Moreno-Diaz. Doctoral thesis, University of Seville, Seville (1998).

  • 99

    , V. Dubois, P. Archirel, A. Boutin. J. Phys. Chem. B 105, 9363 (2001).

    • Crossref
    • Export Citation
  • 100

    , R. Armunanto, C. F. Schwenk, B. M. Rode. J. Phys. Chem. A 107, 3132 (2003).

    • Crossref
    • Export Citation
  • 101

    , Ö. Gröning, T. Drakenberg, L. I. Elding. Inorg. Chem. 21, 1820 (1982).

    • Crossref
    • Export Citation
  • 102

    , A.-V. Mudring, F. Rieger. Inorg. Chem. 44, 6240 (2005) and refs. therein.

    • Crossref
    • Export Citation
  • 103

    , L. Shimoni-Livny, J. P. Glusker, C. W. Bock. Inorg. Chem. 37, 1853 (1998) and refs. therein.

    • Crossref
    • Export Citation
  • 104

    , D. L. Reger, T. D. Wright, C. A. Little, J. J. S. Lamba, M. D. Smith. Inorg. Chem. 40, 3810 (2001).

    • Crossref
    • Export Citation
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