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Zerovalent Organometallics

  1. Andrew W.G. Platt

Published Online: 23 SEP 2013

DOI: 10.1002/9781119951438.eibc2018

Encyclopedia of Inorganic and Bioinorganic Chemistry

Encyclopedia of Inorganic and Bioinorganic Chemistry

How to Cite

Platt, A. W. 2013. Zerovalent Organometallics. Encyclopedia of Inorganic and Bioinorganic Chemistry. 1–6.

Author Information

  1. Staffordshire University, Stoke-on-Trent, UK

Publication History

  1. Published Online: 23 SEP 2013

Abstract

The identification of lanthanide complexes by co-condensation of metal atoms with carbon monoxide in matrix isolation experiments is described. Structures have been suggested on the basis of infrared spectroscopy and theoretical calculations. The reactions on lanthanide atoms with unsaturated aliphatic hydrocarbons led to the isolation of a variety of materials whose exact nature remains uncertain. Cyclooctatetraene forms ionic compounds with Ln3+ ions as a result of its ability to form an aromatic dianion. The formation of bulk quantities of complexes with sterically demanding aromatic hydrocarbons and heteroaromatic compounds leads to sandwich-type complexes. The compounds are thermodynamically stable for many of the lanthanides. The variations in stability have been correlated with the f[RIGHTWARDS ARROW]d promotion energy and the size of the lanthanide atoms. The compounds are all air and moisture sensitive, and other reactions such as substitution and reaction with compounds containing acidic hydrogen are described.

Keywords:

  • zero valent lanthanides;
  • CO complexes;
  • alkene complexes;
  • arene complexes;
  • steric effects;
  • thermodynamic stability;
  • reactions;
  • bonding