Abstract
Even 155 years after their first synthesis, Schiff bases continue to surprise inorganic chemists. Schiff-base ligands have played a major role in the development of modern coordination chemistry because of their relevance to a number of interdisciplinary research fields. The chemistry, properties and applications of transition metal and lanthanoid complexes with Schiff-base ligands are now quite mature. On the contrary, the coordination chemistry of Schiff bases with actinoid (5f-metal) ions is an emerging area, and impressive research discoveries have appeared in the last 10 years or so. The chemistry of actinoid ions continues to attract the intense interest of many inorganic groups around the world. Important scientific challenges are the understanding the basic chemistry associated with handling and recycling of nuclear materials; investigating the redox properties of these elements and the formation of complexes with unusual metal oxidation states; discovering materials for the recovery of trans-{UVIO2}2+ from the oceans; elucidating and manipulating actinoid-element multiple bonds; discovering methods to carry out multi-electron reactions; and improving the 5f-metal ions’ potential for activation of small molecules. The study of 5f-metal complexes with Schiff-base ligands is a currently “hot” topic for a variety of reasons, including issues of synthetic inorganic chemistry, metalosupramolecular chemistry, homogeneous catalysis, separation strategies for nuclear fuel processing and nuclear waste management, bioinorganic and environmental chemistry, materials chemistry and theoretical chemistry. This almost-comprehensive review, covers aspects of synthetic chemistry, reactivity and the properties of dinuclear and oligonuclear actinoid complexes based on Schiff-base ligands. Our work focuses on the significant advances that have occurred since 2000, with special attention on recent developments. The review is divided into eight sections (chapters). After an introductory section describing the organization of the scientific information, Sections 2 and 3 deal with general information about Schiff bases and their coordination chemistry, and the chemistry of actinoids, respectively. Section 4 highlights the relevance of Schiff bases to actinoid chemistry. Sections 5–7 are the “main menu” of the scientific meal of this review. The discussion is arranged according the actinoid (only for Np, Th and U are Schiff-base complexes known). Sections 5 and 7 are further arranged into parts according to the oxidation states of Np and U, respectively, because the coordination chemistry of these metals is very much dependent on their oxidation state. In Section 8, some concluding comments are presented and a brief prognosis for the future is attempted.
Highlights
In the last 10 years or so, there has been a renaissance in the area of the chemistry and properties of metal complexes with Schiff bases as ligands [1]
The topic has been partly covered in some older, excellent reviews or book chapters dealing with the chemistry of actinoids [2,3,4,5,6,7,8,9,10] and the coordination chemistry of Schiff bases [11]
The method that is used to describe the binding of ligands to An ions is the “Harris Notation” [12]. This already widely-accepted method, describes the coordination mode as X.Y1Y2Y3 . . . Yn, where X is the total number of metal ions bound by the whole ligand, and each Y value refers to the number of metal sites attached to the different donor atoms
Summary
In the last 10 years or so, there has been a renaissance in the area of the chemistry and properties of metal complexes with Schiff bases as ligands [1]. This review can be considered as a continuation of the interest of our group in some aspects of An chemistry [13,14,15,16] and coordination chemistry of Schiff bases with 3d [17,18], 4f [19,20,21] and 5f-metal [15,16] ions, with emphasis on dinuclear and polynuclear complexes and their magnetic, optical and catalytic properties. The metals display more than one accessible oxidation state, and one-electron redox chemistry is usual Due to their similar and chemical properties, the partitioning of An and Ln ions (which is very important in nuclear industry) is the most challenging hydrometallurgical separation known. Important scientific challenges for research are handling and recycling nuclear materials, discovering efficient materials for the recovery of {UVIO2}2+ from seawater, investigating the redox properties of these elements, elucidating and manipulating An-elements’ multiple-bond interactions, finding methods to accomplish multi-electron reactions related to organometallic transformations and improving the 5f-elements’ potential in small-molecule activation
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