Ligand Hyperfine Couplings and the Structure of Transition-Metal Complexes
Hyperfine couplings arising from nuclei in the ligands of transition metal complexes have been known for some fifteen years now and have from the first been valuable sources of information on covalency in such species. Within the past few years, however, many new results on ligand hyperfine couplings have been obtained, primarily by ESR. In particular, it has been shown in several systems that the often-invoked back donation or π covalency in cyanides is largely nonexistent, and the detection of ligand hyperfine couplings has verified, in several cases, an energy level scheme which puts the unpaired electron(s) in an orbital which is localized mainly on the ligands. A brief discussion of the detection and analysis of ligand hyperfine couplings will be followed by several examples of interest.
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