The 1992 Alcan Award Lecture Excursions around the periodic table: ligand design in inorganic chemistry

Abstract

An overview is given on the strategy used to come up with the design of a new type of ligand that is appropriate for coordination to both the late metals and the early metals. The coordination chemistry of the potentially tridentate ligand −N(SiMe2CH2PR2)2 is developed starting with the Ni triad and then the heavier members of group 9, namely rhodium and iridium. It is with iridium that reactive fragments such as methylene and vinylidene have been stabilized and their chemistry examined. Extension to groups 3, 4, and the lanthanides is also discussed. With these elements, phosphine coordination imparts new reactivity patterns such as alkane elimination with group 3 and dinitrogen activation with group 4. In addition, the side-on binding mode for N2 attached to a dinuclear zirconium system is also presented.