A continuous symmetry study of the structures of transition metal six-vertex polyhedra is presented, considering both molecular models and experimental structural data. The concept of symmetry map is introduced, consisting of a scatterplot of the symmetry measures relative to two alternative ideal polyhedra. In the case of hexacoordinated complexes, we take as reference shapes the octahedron and the equilateral trigonal prism and study different distortions from these two extremes, including the Bailar twist that interconverts one into another. Such a symmetry map allows us to establish trends in the structural chemistry of the coordination sphere of hexacoordinated transition metal atoms, including the effects of several factors, such as the electron configuration or the presence of bidentate, terdentate or encapsulating ligands. Also introduced is the concept of a symmetry constant, which identifies a distortive route that preserves the minimum distance to two reference
symmetries. A wide variety of model distortions are analyzed, and the models are tested against experimental structural data of a wide variety of six-coordinated complexes.

Continuous symmetry maps and shape classification. The case of six-coordinated metal compounds

Publisher Summary This chapter discusses metal–isocyanide chemistry. In the interim, reviews have appeared on specific aspects of isocyanide chemistry. The generally accepted valence bond and molecular orbital (MO) approach to the bonding of metal isocyanides has been well described in Treichel's review, and has been used to rationalize variations in infrared (IR) stretching frequencies between bonded and nonbonded isocyanides and the better π-acceptor qualities of aryl versus alkyl isocyanide groups. A number of new synthetic routes to isocyanide complexes of chromium, molybdenum, and tungsten have been investigated. A number of attempts have been made over the years to develop reproducible synthetic routes to six- and seven-coordinate isocyanide complexes of molybdenum and tungsten. A number of routes have been employed for the synthesis of metal–isocyanide complexes by generating the isocyanide ligand on the metal atom. A number of monomeric complexes have been prepared, which may be considered as substitution products of the [Co(CNR) 5 ] + and [M(CNR) 4 ] + cations. Electrochemical investigations have been reported on a range of homoleptic and mixed carbonyl–isocyanide complexes, in attempts to rationalize substituent effects on the isocyanide with the electronic structure of the metal. Insertion reactions of isonitriles into metal–alkyl or metal–aryl bonds are now well established, occurring with metal–alkyl or –aryl groups from group IVA to IB and, recently, with uranium and thorium carbon bonds.

Metal Isocyanide Complexes

Coordination chemistry of schiff base complexes of molybdenum

The Coordination and Bioinorganic Chemistry of Molybdenum

Seven‐Coordination Chemistry

Structure of heptakis(tert-butyl isocyanide)molybdenum(II) hexafluorophosphate, a seven-coordinate complex with C2.nu. monocapped trigonal prismatic geometry

David L. Lewis

Papers

Structure of heptakis(tert-butyl isocyanide)molybdenum(II) hexafluorophosphate, a seven-coordinate complex with C2.nu. monocapped trigonal prismatic geometry