Pentanuclear Thorium(IV) Coordination Cluster from the Use of Di(2-pyridyl) Ketone.

The Th(NO3)4·5H2O/di(2-pyridyl) ketone [(py)2CO] reaction system gives a pentanuclear cluster containing the doubly deprotonated form of the gem-diol derivative of the ligand. The cluster consists of a tetrahedral arrangement of four ThIV ions centered on the fifth ion, which is the first characterized ThIV5 complex. The analysis of its structure reveals that this is a Kuratowski-type coordination compound.

Oligonuclear Actinoid Complexes with Schiff Bases as Ligands-Older Achievements and Recent Progress.

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.

Two different coordination modes of the Schiff base derived from ortho-vanillin and 2-(2-aminomethyl)pyridine in a mononuclear uranyl complex.

This work describes the reaction of the potentially tetradentate Schiff-base ligand N-(2-pyridylmethy)-3-methoxysalicylaldimine (HL) with UO2(O2CMe)2·2H2O and UO2(NO3)2· 6H2O in MeOH in the absence or presence of an external base, respectively. The product from these reactions is the mononuclear complex [UO2(L)2] (1). Its structure has been determined by single-crystal, X-ray crystallography. The anionic ligand adopts two different coordination modes (1.1011, 1.1010; Harris notation) in the complex. The new compound was fully characterized by solid-state (IR, Raman and Photoluminescence spectroscopies) and solution (UV-Vis and 1H NMR spectra, conductivity measurements) techniques.

Tetranuclear oxido-bridged thorium(iv) clusters obtained using tridentate Schiff bases.

Thorium(iv) complexes are currently attracting intense attention from inorganic chemists due to the development of liquid-fluoride thorium reactors and the fact that thorium(iv) is often used as a model system for the study of the more radioactive Np(iv) and Pu(iv). Schiff-base complexes of tetravalent actinides are useful for the development of new separation strategies in nuclear fuel processing and nuclear waste management. Thorium(iv)-Schiff base complexes find applications in the colorimetric detection of this toxic metal ion and the construction of fluorescent on/off sensors for Th(iv) exploiting the ligand-based light emission of its complexes. Clusters of Th(iv) with hydroxide, oxide or peroxide bridges are also relevant to the environmental and geological chemistry of this metal ion. The reactions between Th(NO3)4·5H2O and N-salicylidene-o-aminophenol (LH2) and N-salicylidene-o-amino-4-methylphenol (L'H2) in MeCN have provided access to complexes [Th4O(NO3)2(LH)2(L)5] (1) and [Th4O(NO3)2(L'H)2(L')5] (2) in moderate yields. The structures of 1·4MeCN and 2·2.4 MeCN have been determined by single-crystal X-ray crystallography. The complexes have similar molecular structures possessing the {Th4(µ4-O)(µ-OR')8} core that contains the extremely rare {Th4(µ4-O)} unit. The four ThIV atoms are arranged at the vertexes of a distorted tetrahedron with a central µ4-O2- ion bonded to each metal ion. The H atom of one of the acidic -OH groups of each 3.21 LH- or L'H- ligand is located on the imine nitrogen atom, thus blocking its coordination. The ThIV centres are also held together by one 3.221 L2- or (L')2- group and four 2.211 L2- or (L')2- ligands. The metal ions adopt three different coordination numbers (8, 9, and 10) with a total of four coordination geometries (triangular dodecahedral, muffin, biaugmented trigonal prismatic, and sphenocorona). A variety of H-bonding interactions create 1D chains and 2D layers in the crystal structures of 1·4 MeCN and 2·2.4 MeCN, respectively. The structures of the complexes are compared with those of the uranyl complexes with the same or similar ligands. Solid-state and IR data are discussed in terms of the coordination mode of the organic ligands and the nitrato groups. 1H NMR data suggest that solid-state structures are not retained in DMSO. The solid complexes emit green light at room temperature upon excitation at 400 nm, the emission being ligand-centered.

Binding of oxime group to uranyl ion.

Currently, the leading approach for extraction of uranium from seawater is selective sorption of UO2(2+) ions onto a poly(acrylamidoxime) fiber. Amidoxime functional groups are the most studied extractant moieties for this application, but are not perfectly selective, and understanding how these groups (and more generally the oxime groups) interact with UO2(2+) and competing ions in seawater is an important step in designing better extractants. We have started a new research programme aiming at in-depth studies of the uranyl-oxime/amidoxime interactions and we report here our first results which cover aspects of the coordination chemistry of 2-pyridyl ketoximes towards UO2(2+). Detailed synthetic investigations of various UO2(2+)/mepaoH and UO2(2+)/phpaoH reaction systems (mepaoH is methyl 2-pyridyl ketoxime and phpaoH is phenyl 2-pyridyl ketoxime) have provided access to the complexes [UO2(mepao)2(MeOH)2]{[UO2(NO3)(mepao)(MeOH)2]}2 (), [UO2(mepao)2(MeOH)2] (), [(UO2)2(O2)(O2CMe)2(mepaoH)2] () and [UO2(phpao)2(MeOH)2] (). The peroxido group in , which was isolated without the addition of external peroxide sources, probably arises from a bis(aquo)- and/or bis(hydroxido)-bridged diuranyl precursor in solution followed by photochemical oxidation of the bridging groups. The U(VI) atom in the [UO2(NO3)(mepao)(MeOH)2] molecules of () is surrounded by one nitrogen and seven oxygen atoms in a very distorted hexagonal bipyramidal geometry; two oxygen atoms from the terminal MeOH ligands, two oxygen atoms from the bidentate chelating nitrato group, and the oxygen and nitrogen atoms from the η(2) oximate group of the 1.110 (Harris notation) mepao(-) ligand define the equatorial plane. This plane consists of two terminal MeOH ligands and two η(2) oximate groups in the [UO2(mepao)2(MeOH)2] molecule () of . The structure of the [UO2(mepao)2(MeOH)2] molecule that is present in is very similar to the structure of the corresponding molecule in . The structure of the dinuclear molecule that is present in consists of two {UO2(O2CMe)(mepaoH)}(+) units bridged by a η(2):η(2):µ O2(2-) group. The equatorial plane of each uranyl site is composed of the pyridyl and oxime nitrogen atoms of a 1.011 mepaoH ligand, the oxygen atoms of an almost symmetrically coordinated bidentate chelating MeCO2(-) group and the two oxygen atoms of the peroxido groups. The core molecular structure of is similar to that of , the only difference being the presence of 1.110 phpao(-) ligands in the former instead of mepao(-) groups in the latter. The free pyridyl nitrogen atoms of mepao(-) and phpao(-) ligands of , and are acceptors of intramolecular H bonds from the ligated MeOH oxygen atoms. H-bonding and π-π stacking interactions build interesting supramolecular networks in the crystal structures of the four complexes. Compounds are the first structurally characterized uranyl complexes with 2-pyridyl aldoximes or ketoximes as ligands. IR data are discussed in terms of the coordination modes of the ligands in the complexes. (1)H NMR data in DMSO-d6 suggest that the complexes decompose in solution. The ESI(-) MS spectrum of dissolved in the NH4(O2CMe) buffer is indicative of the presence of [UO2(O2CMe)3](-), [UO2(O2CMe)2(phpao)](-), [UO2(O2CMe)(phpao)2](-) and [UO2(phpao)3](-) species. A common structural motif of the complexes containing the anionic mepao(-) (, ) and phpao(-) () ligands is that the deprotonated oximate group prefers to bind in the η(2) fashion forming a 3-membered chelating ring in spite of the presence of a pyridyl nitrogen atom, whose coordination would be expected to lead to 5- or 6-membered chelating rings.