Abstract
This review covers the activation of molecular pnictogens (group 15 elements) by homogeneous rare earth and actinide complexes. All examples of molecular pnictogen activation (dinitrogen, white phosphorus, yellow arsenic) by both rare earths and actinides, to date (2015), are discussed, focusing on synthetic methodology and the structure and bonding of the resulting complexes.
Highlights
Rare earth and actinide complexes remain underexplored with respect to the transition metals and main group elements but often demonstrate both unique reactivity and molecular properties
This review seeks to cover all examples of molecular pnictogen activation by both rare earth and actinide complexes to date, focusing on synthetic methodology and the structure and bonding of the resulting complexes
Compared to both rare earth and actinide complexes, the activation of P4 by transition metal complexes have proven to result in a wide variety of activation products [58,59]; with notable examples including fragmentation resulting in terminal and bridging P1 ligands [135,136,137], P2 ligands [138], cyclo-P3 ligands [56,139], fragmentation to other P4 ligands [140], coordination of P4 tetrahedra [141,142], and expansion to Pn (n = 5–14) ligands [143,144,145,146]
Summary
Rare earth (scandium, yttrium and the lanthanides) and actinide complexes remain underexplored with respect to the transition metals and main group elements but often demonstrate both unique reactivity and molecular properties. The Haber–Bosch process combines N2 and high purity H2 at high temperatures and pressures over heterogeneous iron- or ruthenium-based catalysts [7,8,9,10] This highly efficient process produces 100 million tons of ammonia per year but is the largest energy-consuming process in the modern world today; the need for direct activation and functionalisation of N2 under mild conditions is a clear goal. This review seeks to cover all examples of molecular pnictogen activation (dinitrogen, white phosphorus, yellow arsenic) by both rare earth and actinide complexes to date, focusing on synthetic methodology and the structure and bonding of the resulting complexes. Well-defined homogeneous complexes will be discussed; heterogeneous and surface chemistry lie beyond the scope of this review
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