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Structural Organomanganese Chemistry

Organomanganese Compounds (2011)

  1. Ryan M. Meier,
  2. Timothy P. Hanusa

Published Online: 15 JUL 2011

DOI: 10.1002/9780470682531.pat0541

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Meier, R. M. and Hanusa, T. P. 2011. Structural Organomanganese Chemistry. Patai's Chemistry of Functional Groups. .

Author Information

  1. Vanderbilt University, Department of Chemistry, Tennessee, USA

Publication History

  1. Published Online: 15 JUL 2011

Abstract

In the more than 50 years since the first manganese compound with Mn[BOND]C bonds was crystallographically characterized (Mn2(CO)10, in 1957), the number of structurally authenticated organomanganese compounds has grown to several thousands. The richness of structural features in organomanganese compounds now rivals that of any other first row transition metal. The range of structural features and bond types is large, and encompasses Mn[BOND]C, Mn[DOUBLE BOND]C, and Mn[TRIPLE BOND]C bonds, as well as complexes with Mn[BOND]Mn, Mn[DOUBLE BOND]Mn, and Mn[TRIPLE BOND]Mn linkages. Crystallographically characterized examples are known with oxidation states from Mn0 to MnV, and the accessibility of two spin states of comparable energy in complexes of MnII adds an additional variable to the fundamental structural types. The present review of structural organomanganese chemistry focuses largely on crystallographically characterized complexes, whose geometries are the most reliably established. Representative examples of major compound classes are considered, and statistical analysis of typical bond length ranges is provided for various Mn/C and Mn/Mn interactions. Bond lengths in organomanganese compounds are highly context-sensitive, and even when only a specific bond order is under consideration, the spread of distances makes comparisons difficult unless closely related molecules are examined.

Keywords:

  • cyclopentadienyl complexes;
  • cymantrene;
  • manganese;
  • manganocene;
  • organometallic chemistry;
  • paramagnetic compounds;
  • solid-state structures;
  • spin states;
  • steric bulk;
  • X-ray crystallography