Cyano- and halogeno-bridged transition-metal complexes. Structural comparisons of neutral and cationic oligomers

Abstract

The structures of some neutral and cationic oligomeric transition-metal complexes with bridging Cl and CN groups are discussed. Application of the method of structural fragments leads to the expectation of bent M–Cl–M and linear M–CN–M bridges in oligomeric complexes, resulting in the formation of dimeric chloride-bridged complexes and tetrameric cyanide-bridged complexes. These structures are found for neutral oligomers, but for charged species an additional electrostatic repulsion term is shown to be an important factor in determining the degree of oligomerization.