Closed-Shell Systems, Hydrides and Back-Bonding

  • Chr. Klixbüll Jørgensen
Part of the Molekülverbindungen und Koordinationsverbindungen in Einzeldarstellungen book series (MOLEKÜL)


Once the spectroscopic oxidation states have been firmly established for nearly all systems containing partly filled f shells and most systems containing partly filled d shells, we are in the rather paradoxical situation that the classification of closed-shell systems is more uncertain and to some extent derived by analogy. Thus, there is no serious doubt that the colourless copper (I), zinc (II), gallium (III) and germanium (IV) compounds are d10-systems with the completely filled M. O. well separate energy-wise from the empty M. O. However, one already runs into a problem when considering ligands specializing in forming low oxidation states of the central atom, such as CO or PF3 when entering colourless iron (— II), cobalt (— I) and nickel (0) complexes. Professor K. A. Jensen once, half seriously, suggested that Ni(CO)4 is a nickel (VIII) compound of the ligand C−− formed by complete deprotonation of monomeric formaldehyde H2CO. This rather extreme example illustrates a very important point about complexes having no low-lying excited levels: if there is any doubt about the oxidation state of the ligands, the acceptable values usually jump by two units with the result that the oxidation state of the central atom jumps 2N units if N ligands occur. Thus, V(CO) 6 and Cr(CO)6 would involve V(XI) and Cr (XII) if the description as CO−− complexes was assumed, which is entirely unacceptable. In this connection, it may be mentioned that the highest oxidation state known is +8 in the tetroxides and a few other oxo-complexes of Ru(VIII), Xe(VIII) and Os(VIII). The element having the greatest chance of being further oxidized would be iridium (IX) conceivably forming IrO3F3 or salts of IrFs 6 + 3 of non-oxidizable anions providing a large Madelung potential such as SiFs 6 −− (cf. Jørgensen, 1963).


Central Atom Lewis Base Nitrosyl Complex Hydride Complex Verdet Constant 
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© Springer-Verlag Berlin Heidelberg 1969

Authors and Affiliations

  • Chr. Klixbüll Jørgensen
    • 1
  1. 1.Cyanamid European Research InstituteCologny, GenevaSwitzerland

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