Abstract
The molecular chemistry of the f-elements, i.e. the lanthanides and actinides, is traditionally dominated by the use of carbon, nitrogen, oxygen or halide ligands. However, the use of metal-based fragments as ligands is underdeveloped, which contrasts to the field of d-block metal–metal complexes that have developed extensively over the last 50 years. Consequently, the use of metal-based fragments as ligands to the f-elements may be regarded as ‘non-traditional’. This review outlines the development of compounds that possess f-element–metal bonds that may be described as polarized covalent or donor–acceptor in nature. For this review, the f-element is defined as (i) a group 3 or lanthanide metal: scandium, yttrium and lanthanum to lutetium or (ii) an actinide metal: thorium or uranium, and the metal is defined as a d-block transition metal, or a p-block triel (group 13, aluminium or gallium), a tetrel (group 14, silicon, germanium or tin), or a pnictide (group 15, antimony or bismuth) metal. Silicon, germanium and antimony are traditionally classified as metalloids, but we include them in this review for completeness. This review focuses on complexes that have been unambiguously structurally authenticated by single crystal X-ray diffraction studies, and novel aspects of their syntheses, properties and reactivities are highlighted.
Highlights
The f-elements are traditionally described as hard electropositive ions that preferentially bind to hard Lewis basic ligands
We present a review of the emerging area of f-element–metal bonds, focusing principally on complexes that have been unambiguously structurally authenticated by single crystal X-ray diffraction studies, and we highlight novel aspects of their syntheses, properties and reactivities
Under C3v symmetry, the d10 [Fe(CO)4]2K dianion formally possesses a lone pair directed towards an axial site, which results in the coordination sphere of ytterbium being further supplemented by an Fe/Yb dative donor–acceptor interaction that forms the rungs of the ladders by linking the two strands of the ladder together
Summary
The f-elements are traditionally described as hard electropositive ions that preferentially bind to hard Lewis basic ligands. The uranyl [UO2]2C unit accounts for more than 60 per cent of all structurally characterized molecular uranium complexes Since these ligand classes are dominant, they may be referred to as traditional in nature. Given the paucity of f-element–metal chemistry, and the advances that have historically resulted from investigating metal–metal chemistry, the study of f-element–metal bonds represents an excellent opportunity to advance our understanding of chemical bonding and catalysis at the foot of the periodic table. This is of direct relevance to the remediation of nuclear waste and the design of new and more efficient catalytic cycles. We present a review of the emerging area of f-element–metal bonds, focusing principally on complexes that have been unambiguously structurally authenticated by single crystal X-ray diffraction studies, and we highlight novel aspects of their syntheses, properties and reactivities
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