Insights into the Chemistry of Transient P-Chlorophosphanyl Complexes

摘要

Main-group-element compounds with one or more unpaired electrons have emerged as a fascinating research topic in recent years.The fundamental breakthrough in the area of phosphorus-based radicals with low-coordinate phosphorus centers was achieved by M. F. Lappert et al. with the synthesis of the first stable derivative of type I (R = CH(SiMe3)2), which dimerizes (reversibly) upon crystallization. This compound has been used as a ligand in cobalt and iron carbonyl complexes. More recently, heteroatom-substituted derivatives of II and in have been synthesized (Scheme 1). Interesting follow-up reactions involving rearrangement and decomposition processes of III have been observed. In contrast, knowledge about derivatives IV, which have potential leaving groups, is extremely scarce and, to the best of our knowledge, its coordination chemistry is unknown. The latter is of special interest, as open-shell complexes have been recognized as highly interesting targets, for example as contrast agents for molecular imaging.