2 + 1 Tricarbonyl Complexes of Technetium(I) with a Combination of N,N-Bidentate Ligands and Ethyl Isocyanoacetate: How Strong Is the Interfering Effect of Chloride Ions on Their Formation?

Technetium(I) 2 + 1 tricarbonyl complexes with a combination of N,N-bidentate ligands (2,2'-bipyridine, bipy; 1,10-phenanthroline, phen) and ethyl isocyanoacetate were prepared and characterized by NMR, IR, UV/visible, and luminescence spectroscopies and by high-performance liquid chromatography (HPLC). The crystal structures of [99Tc(CO)3(bipy)(CNCH2COOEt)](ClO4) (in the form of a solvate with 0.5CH2Cl2) and [99Tc(CO)3(phen)(CNCH2COOEt)](ClO4) (in the form of an adduct with an outer-sphere phen molecule) were determined by single-crystal X-ray diffraction. To evaluate the interfering effect of chloride ions on the formation of the 2 + 1 complexes, the kinetics of the replacement of labile monodentate ligand X in the complexes [MX(CO)3(N∧N)] (M = Re, 99Tc; N∧N = bipy, phen; X = Cl-, ClO4-) by CNCH2COOEt in ethanol were compared. The 99Tc bipy complexes with X = ClO4- (according to the IR data, perchlorate anion in ethanol is displaced from the coordination sphere by the solvent molecule) and X = Cl- are characterized by close ligand replacement rates. In the case of the 99Tc complexes with phen and Re complexes with both phen and bipy, the chloride complexes are appreciably less reactive than the chloride-free complexes. The technetium complexes are considerably more reactive in ligand replacement than their rhenium analogues. In the chloride-containing medium (saline), the complex [99mTc(CO)3(bipy)(CNCH2COOEt)]+ can be prepared under the conditions acceptable for nuclear medical applications, although higher isonitrile concentrations are required as compared to the chloride-free system.

Unusual Effects of the Metal Center Coordination Mode on the Photophysical Behavior of the Rhenium(I) and Rhenium(I)-Iridium(III) Complexes.

Binuclear transition-metal complexes based on conjugated systems containing coordinating functions are potentially suitable for a wide range of applications, including light-emitting materials, sensors, light-harvesting systems, photocatalysts, etc., due to energy-transfer processes between chromophore centers. Herein we report on the synthesis, characterization, photophysical, and theoretical studies of relatively rare rhenium(I) and rhenium(I)-iridium(III) dyads prepared by using the nonsymmetrical polytopic ligands (NN2 and NN3) with the strongly conjugated phenanthroline and imidazole-quinoline/pyridine coordinating fragments. Availability of these different diimine chelating functions and targeted synthetic procedures allowed one to obtain a series of mononuclear (Re and Ir) and binuclear (Re-Re and Re-Ir) metal complexes with various modes of {Re(CO)3Cl} and {Ir(NC)2} metal fragment coordination. The obtained compounds were characterized by 1D 1H and 2D (COSY and NOESY) NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction crystallography. The photophysical study of the complexes (absorption, excitation and emission spectra, quantum yields, and excited-state lifetimes) showed that their emission parameters display strong dependence on the manner of metal center coordination to the diimine bidentate functions. The mononuclear complexes with an unoccupied imidazole-quinoline/pyridine fragment [Re(NN2), Re(NN3), and Ir(NC2)2(NN2)] or those containing a coordinated {Ir(NC)2} fragment in this position [Ir(NC2)2(NN1) and Re(NN2)Ir(NC1)2-Re(NN2)Ir(NC4)2] exhibit moderate-to-intense phosphorescence (quantum yields vary from 3% to 56% in a degassed solution), whereas the complexes containing a {Re(CO)3Cl} moiety in the imidazole-quinoline/pyridine position [Re2(NN2), Re2(NN3), and Ir(NC2)2(NN2)Re] demonstrate a strong reduction in the phosphorescence efficiency with a quantum yield of ≪0.1%. Quenching of the phosphorescence in the latter types of emitters is discussed in terms of a strong decrease in the radiative rate constants for these complexes compared to their analogues mentioned above, while the nonradiative constants remain nearly unchanged. Theoretical density functional theory (DFT) and time-dependent DFT (TD DFT) calculations, including evaluation of the radiative rate constants for the couple of structurally analogous complexes with and without a {Re(CO)3Cl} moiety coordinated to the imidazole-quinoline/pyridine chelating function, confirmed the observed trend in the variation of the emission intensity.

Organically Templated Uranyl Sulfates and Selenates: Structural Complexity and Crystal Chemical Restrictions for Isotypic Compounds Formation.

This paper reviews the state of the art in the structural chemistry of organically templated uranyl sulfates and selenates, which are considered as the most representative groups of U-bearing synthetic compounds. In total, there are 194 compounds known for both groups, the crystal structures of which include 84 various organic molecules. Structural studies and topological analysis clearly indicate complex crystal chemical limitations in terms of the isomorphic substitution implementation, since the existence of isotypic phases has to date been confirmed only for 24 compounds out of 194, which is slightly above 12%. The structural architecture of the entire compound depends on the combination of the organic and oxyanion parts, changes in which are sometimes realized even while maintaining the topology of the U-bearing complex. An increase in the size of the hydrocarbon part and number of charge functional groups of the organic cation leads to the formation of rare and more complex topologies. In addition, the crystal structures of two novel uranyl sulfates and one uranyl selenate, templated by isopropylammonium cations, are reported.

Crystal Chemistry of the Copper Oxalate Biomineral Moolooite: The First Single-Crystal X-ray Diffraction Studies and Thermal Behavior.

Moolooite, Cu(C2O4)·nH2O, is a typical biomineral which forms due to Cu-bearing minerals coming into contact with oxalic acid sources such as bird guano deposits or lichens, and no single crystals of moolooite of either natural or synthetic origin have been found yet. This paper reports, for the first time, on the preparation of single crystals of a synthetic analog of the copper-oxalate biomineral moolooite, and on the refinement of its crystal structure from the single-crystal X-ray diffraction (SCXRD) data. Along with the structural model, the SCXRD experiment showed the significant contribution of diffuse scattering to the overall diffraction data, which comes from the nanostructural disorder caused by stacking faults of Cu oxalate chains as they lengthen. This type of disorder should result in the chains breaking, at which point the H2O molecules may be arranged. The amount of water in the studied samples did not exceed 0.15 H2O molecules per formula unit. Apparently, the mechanism of incorporation of H2O molecules governs the absence of good-quality single crystals in nature and a lack of them in synthetic experiments: the more H2O content in the structure, the stronger the disorder will be. A description of the crystal structure indicates that the ideal structure of the Cu oxalate biomineral moolooite should not contain H2O molecules and should be described by the Cu(C2O4) formula. However, it was shown that natural and synthetic moolooite crystals contain a significant portion of "structural" water, which cannot be ignored. Considering the substantially variable amount of water, which can be incorporated into the crystal structure, the formula Cu(C2O4)·nH2O for moolooite is justified.

Hydrolysis of Hexacarbonyltechnetium(I) Cation: Formation and Structure of Technetium Carbonyl Hydride 99Tc3H(CO)14.

Reaction of [99Tc(CO)6]ClO4 with alkali in aqueous solutions yields yellow 99Tc3H(CO)14 as the major product. On the other hand, [99TcH(CO)5] becomes the major product when the reaction with alkali is combined with the extraction into hexane. The molecular structure of 99Tc3H(CO)14, determined by SCXRD, is composed of the 99Tc2(CO)9 fragment bound to the 99Tc(CO)5 fragment via the hydrogen bridge and weak metal-metal bond. This compound crystallizes in the monoclinic system, space group P21/n, a = 9.6954(2) Å, b = 15.0985(3) Å, c = 14.5090(3) Å, and ß = 104.925(2)°. 99Tc3H(CO)14 was additionally characterized by IR spectroscopy. The mechanism of hydrolysis of [99Tc(CO)6]ClO4 was suggested.

Binuclear Gold(I) Phosphine Alkynyl Complexes Templated on a Flexible Cyclic Phosphine Ligand: Synthesis and Some Features of Solid-State Luminescence.

A flexible bidentate cyclic phosphine, namely, 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP), was used as a template to construct a family of binuclear heteroleptic phosphine alkynyl complexes [PNNP(AuC2R)2], with R = Ph, C6H10OH, C5H8OH, (CH3)2COH, Ph2COH. All complexes obtained were characterized by CHN elemental analysis, NMR spectroscopy, and single-crystal X-ray analysis. It was found that the gold(I) complexes demonstrate a different organization of the crystal structure depending on the nature of the cocrystallized solvent (dichloromethane, acetone, and acetonitrile) because of formation of the supramolecular complexes through hydrogen bonding. These weak interactions appear to determine the conformation, packing, and spatial cooperation of flexible complex molecules that are reflected in the photophysical properties, which were carefully investigated in solution and in the solid state. The complexes demonstrate weak emission in solution at room temperature, and freezing results in blue shifting of the emission, which is accompanied by a significant increase in the luminescence intensity. Being isolated from dichloromethane, all gold(I) complexes exhibit green phosphorescence in the solid state, and the complexes with R = Ph and Ph2COH display substantial variation of their emission color after recrystallization from acetone and acetonitrile, respectively, which manifests itself as a significant bathochromic shift of up to 120 nm. The structural nonrigidity of the gold(I) complexes obtained and its impact on the properties of low-energy excited states were investigated in detail by density functional theory calculations, which indicate the significant role of the structural flexibility of the PNNP ligand in the formation of the low-energy excited states and confirm the impact of rotation of the functional groups in the coordination sphere on the emission properties of complexes.

Synthesis of 3(2)-phosphonylated thiazolo[3,2-a]oxopyrimidines.

A series of 3(2)-phosphonylated thiazolo[3,2-a]oxopyrimidines was synthesized for the first time by the reactions of chloroethynylphosphonates with unsubstituted and 5(6)-substituted 2-thiouracils. The reaction of chloroethynylphosphonates with 6-substituted 2-thiouracils bearing electron-donor groups (CH3, Ph) proceeded with high regioselectivity involving the cyclization through the N3-nitrogen atom to form new 3-phosphonylated thiazolo[3,2-a]-5-oxopyrimidines with good yield. In the case of unsubstituted and 5-methyl-2-thiouracils, cyclization occurred predominantly through the N1 atom and partially via the N3-nitrogen atom to form a mixture of the corresponding thiazolo[3,2-a]-7- and 5-oxopyrimidines. A dramatic change in the reaction regioselectivity was observed in the case of 6-trifluoromethyl-2-thiouracil that afforded 2- and 3-phosphonylated 5-oxothiazolopyrimidines in a 1:1 ratio.

Chemically Induced Polytypic Phase Transitions in the Mg[(UO2)(TO4)2(H2O)](H2O)4 (T = S, Se) System.

Chemically induced polytypic phase transitions have been observed during experimental investigations of crystallization in the mixed uranyl sulfate-selenate Mg[(UO2)(TO4)2(H2O)](H2O)4 (T = S, Se) system. Three different structure types form in the system, depending upon the Se:S ratio in the initial aqueous solution. The phases with the Se/(Se + S) ratios (in mol %) in the ranges 0-9, 16-47, and 58-100 crystallize in the space groups P21, Pmn21, and P21/c, respectively. The structures of the phases are based upon the same type of uranyl-based sulfate/selenate chains that, through hydrogen bonds, are linked into pseudolayers of the same topological type. The layers are linked into three-dimensional structures via interlayer Mg-centered octahedra. The three structure types contain the same layers but with different stacking sequences that can be conveniently described as belonging to the 1M, 2O, and 2M polytypic modifications. The Se-for-S substitution demonstrates a strong selectivity with preferential incorporation of Se into less tightly bonded T1 site. The larger ionic radius of Se6+ relative to S6+ induces rotation of (T1O4) tetrahedra in the adjacent layers and reconstruction of the structure types. From the information-theoretic viewpoint, the intermediate Pmn21 structure type is more complex than the monoclinic end-member structure types.

Reactions of Cyclometalated Platinum(II) [Pt(N∧C)(PR3)Cl] Complexes with Imidazole and Imidazole-Containing Biomolecules: Fine-Tuning of Reactivity and Photophysical Properties via Ligand Design.

This work describes interaction of a family of [Pt(N∧C)(PR3)Cl] complexes with imidazole (Im), possible application of this chemistry for regioselective labeling of proteins through imidazole rings of histidine residues and employment of the resulting phosphorescent products in bioimaging. It was found that the complexes containing aliphatic phosphines display reversible substitution of chloride ligand for imidazole function that required considerable excess of imidazole to obtain full conversion into the substituted [Pt(ppy)(PR3)(Im)] product, whereas the substitution in the complexes with aromatic phosphines readily proceeds in 1:1.5 mixture of reagents. Rapid, selective, and quantitative coordination of imidazole to the platinum complexes enabled regioselective labeling of ubiquitin. X-ray protein crystallography of the {[Pt(ppy)(PPh3)]/ubiquitin} conjugate revealed direct bonding of the platinum center to unique histidine-68 residue through the nitrogen atom of imidazole function, the coordination being also supported by noncovalent interaction of the ligands with the protein secondary structure. The variations of the cyclometalating N∧C ligands gave a series of [Pt(N∧C)(PPh3)Cl] complexes (N∧C = 2-phenylpyridine, 2-(benzofuran-3-yl)pyridine, 2-(benzo[b]thiophen-3-yl)pyridine, methyl-2-phenylquinoline-4-carboxylate), which were used to investigate the impact of N∧C-ligand onto photophysical properties of the imidazole complexes and conjugates with human serum albumin (HSA). The chloride ligand substitution for imidazole and formation of the conjugates results in ignition of the platinum chromophore luminescence with substantially higher quantum yield in the latter case. Variation of the metalating N∧C-ligand made possible the shift of the emission to the red region of visible spectrum for both types of the products. Cell-viability tests revealed low cytotoxicity of all {[Pt(N∧C)(PPh3)Cl]/HSA} conjugates, while PLIM experiments demonstrated their high potential for oxygen sensing.

Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores.

Combining the star-shaped alkynyl ligands with low-nuclearity gold-copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem =0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

Coordination to Imidazole Ring Switches on Phosphorescence of Platinum Cyclometalated Complexes: The Route to Selective Labeling of Peptides and Proteins via Histidine Residues.

In this study, we have shown that substitution of chloride ligand for imidazole (Im) ring in the cyclometalated platinum complex Pt(phpy)(PPh3)Cl (1; phpy, 2-phenylpyridine; PPh3, triphenylphosphine), which is nonemissive in solution, switches on phosphorescence of the resulting compound. Crystallographic and nuclear magnetic resonance (NMR) spectroscopic studies of the substitution product showed that the luminescence ignition is a result of Im coordination to give the [Pt(phpy)(Im)(PPh3)]Cl complex. The other imidazole-containing biomolecules, such as histidine and histidine-containing peptides and proteins, also trigger luminescence of the substitution products. The complex 1 proved to be highly selective toward the imidazole ring coordination that allows site-specific labeling of peptides and proteins with 1 using the route, which is orthogonal to the common bioconjugation schemes via lysine, aspartic and glutamic acids, or cysteine and does not require any preliminary modification of a biomolecule. The utility of this approach was demonstrated on (i) site-specific modification of the ubiquitin, a small protein that contains only one His residue in its sequence, and (ii) preparation of nonaggregated HSA-based Pt phosphorescent probe. The latter particles easily internalize into the live HeLa cells and display a high potential for live-cell phosphorescence lifetime imaging (PLIM) as well as for advanced correlation PLIM and FLIM experiments.

Supramolecular Au(I)-Cu(I) Complexes as New Luminescent Labels for Covalent Bioconjugation.

Two new supramolecular organometallic complexes, namely, [Au6Cu2(C2C6H4CHO)6(PPh2C6H4PPh2)3](PF6)2 and [Au6Cu2(C2C6H4NCS)6(PPh2C6H4PPh2)3](PF6)2, with highly reactive aldehyde and isothiocyanate groups have been synthesized and characterized using X-ray crystallography, ESI mass spectrometry, and NMR spectroscopy. The compounds obtained demonstrated bright emission in solution with the excited-state lifetime in microsecond domain both under single- and two-photon excitation. The luminescent complexes were found to be suitable for bioconjugation in aqueous media. In particular, they are able to form the covalent conjugates with proteins of different molecular size (soybean trypsin inhibitor, human serum albumin, rabbit anti-HSA antibodies). The conjugates demonstrated a high level of the phosphorescent emission from the covalently bound label, excellent solubility, and high stability in physiological media. The highest quantum yield, storage stability, and luminance were detected for bioconjugates formed by covalent attachment of the aldehyde-bearing supramolecular Au(I)-Cu(I) complex. The measured biological activity of one of the labeled model proteins clearly showed that introduced label did not prevent the biorecognition and specific protein-protein complex formation that was extremely important for the application of the conjugates in biomolecular detection and imaging.

Aurophilicity in Action: Fine-Tuning the Gold(I)-Gold(I) Distance in the Excited State To Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)-NHC Complexes.

The solution-state emission profiles of a series of dinuclear Au(I) complexes 4-6 of the general formula Au2(NHC-(CH2)n-NHC)2Br2, where NHC = N-benzylbenzimidazol-2-ylidene and n = 1-3, were found to be markedly different from each other and dependent on the presence of excess bromide. The addition of excess bromide to the solutions of 4 and 6 leads to red shifts of ca. 60 nm, and in the case of 5, which is nonemissive when neat, green luminescence emerges. A detailed computational study undertaken to rationalize the observed behavior revealed the determining role aurophilicity plays in the photophysics of these compounds, and the formation of exciplexes between the complex cations and solvent molecules or counterions was demonstrated to significantly decrease the Au-Au distance in the triplet excited state. A direct dependence of the emission wavelength on the strength of the intracationic aurophilic contact allows for a controlled manipulation of the emission energy by varying the linker length of a diNHC ligand and by judicial choice of counterions or solvent. Such unique stimuli-responsive solution-state behavior is of interest to prospective applications in medical diagnostics, bioimaging, and sensing. In the solid, the investigated complexes are intensely phosphorescent and, notably, 5 and 6 exhibit reversible luminescent mechanochromism arising from amorphization accompanied by the loss of co-crystallized methanol molecules. The mechano-responsive properties are also likely to be related to changes in bromide coordination and the ensuing alterations of intramolecular aurophilic interactions. Somewhat surprisingly, the photophysics of NHC ligand precursors 2 and 3 is related to the formation of ground-state associates with bromide counterions through hydrogen bonding, whereas 1 does not appear to bind its counterions.

Luminescence Solvato- and Vapochromism of Alkynyl-Phosphine Copper Clusters.

The reaction of [Cu(NCMe)4][PF6] with aromatic acetylenes HC2R and triphosphine 1,1,1-tris(diphenylphosphino)methane in the presence of NEt3 results in the formation of hexanuclear Cu(I) clusters with the general formula [Cu6(C2R)4{(PPh2)3CH}2][PF6]2 (R = 4-X-C6H4 (1-5) and C5H4N (6); X = NMe2 (1), OMe (2), H (3), Ph (4), CF3 (5)). The structural motif of the complexes studied consists of a Cu6 metal core supported by two phosphine ligands and stabilized by σ- and π-coordination of the alkynyl fragments (together with coordination of pyridine nitrogen atoms in cluster 6). The solid state structures of complexes 2-6 were determined by single crystal XRD analysis. The structures of the complexes in solution were elucidated by (1)H, (31)P, (1)H-(1)H COSY NMR spectroscopy, and ESI mass spectrometry. Clusters 1-6 exhibit moderately strong phosphorescence in the solid state with quantum yields up to 17%. Complexes 1-5 were found to form solvates (acetone, acetonitrile) in the solid state. The coordination of loosely bound solvent molecules strongly affects emission characteristics and leads to solvato- and vapochromic behavior of the clusters. Thus, solvent-free and acetonitrile solvated forms of 3 demonstrate contrasting emission in orange (615 nm) and blue (475 nm) regions, respectively. The computational studies show that alkynyl-centered IL transitions mixed with those of MLCT between the Cu6 metal core and the ligand environment play a dominant role in the formation of excited states and can be considerably modulated by weakly coordinating solvent molecules leading to luminescence vapochromism.

Regio- and Stereoselective 1,3-Dipolar Cycloaddition of Cyclic Azomethine Imines to Platinum(IV)-Bound Nitriles Giving Δ(2)-1,2,4-Triazoline Species.

The complex trans-[PtCl4(EtCN)2] (14) reacts smoothly at 25 °C with the stable cyclic azomethine imines R(1)CH═N(a)NC(O)CH(NHC(O)C6H4R(3))C(b)H(C6H4R(2))((a-b)) [R(1)/R(2)/R(3) = p-Me/H/H (8); p-Me/p-Me/H (9); p-Me/p-MeO/H (10); p-Me/p-Cl/p-Cl (11); p-MeO/p-Me/H (12); p-MeO/p-Cl/m-Me (13)], and the reaction proceeds as stereoselective 1,3-dipolar cycloaddition to one of the EtCN ligands accomplishing the monocycloadducts trans-[PtCl4(EtCN){N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1)}])((a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (15); p-Me/p-Me/H (16); p-Me/p-MeO/H (17); p-Me/p-Cl/p-Cl (18); p-MeO/p-Me/H (19); p-MeO/p-Cl/m-Me (20)]. Inspection of the obtained and literature data indicate that the cycloaddition of the azomethine imines to the C≡N bonds of HCN and of Pt(IV)-bound EtCN has different regioselectivity leading to Δ(2)-1,2,3-triazolines and Δ(2)-1,2,4-triazolines, respectively. Platinum(II) species trans-[PtCl2(EtCN){N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1)}]((a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (21); p-Me/p-Me/H (22); p-Me/p-MeO/H (23); p-Me/p-Cl/p-Cl (24); p-MeO/p-Me/H (25); p-MeO/p-Cl/m-Me (26)] were obtained by a one-pot procedure from 14 and 8-13 followed by addition of the phosphorus ylide Ph3P═CHCO2Me. Δ(2)-1,2,4-Triazolines N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1(a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (27); p-Me/p-Me/H (28); p-Me/p-MeO/H (29); p-Me/p-Cl/p-Cl (30); p-MeO/p-Me/H (31); p-MeO/p-Cl/m-Me (32)] were liberated from 21-26 by the treatment with bis(diphenylphosphyno)ethane (dppe). Platinum(II) complexes 21-26 were characterized by elemental analyses (C, H, N), high-resolution electrospray ionization mass spectrometry (ESI-MS), and IR and (1)H and (13)C{(1)H} NMR spectroscopies and single crystal X-ray diffraction in the solid state for 25·CH3OH, 26·(CHCl3)0.84. The structure of 26 was also determined by COSY-90 and NOESY NMR methods in solution. Quantitative evaluation of several pairs of interproton distances obtained by NMR and X-ray diffraction agrees well with each other and with those obtained by the MM+ calculation method. Platinum(IV) complexes 15-20 were characterized by (1)H NMR spectroscopy. Metal-free 6,7-dihydropyrazolo[1,2-a][1,2,4]triazoles (27-32) were characterized by high-resolution ESI-MS and IR and (1)H and (13)C{(1)H} NMR spectroscopies and single crystal X-ray diffraction for 29·CDCl3. Theoretical density functional theory calculations were carried out for the investigation of the reaction mechanism, interpretation of the reactivity of Pt-bound and free nitriles toward azomethine imines and analysis of the regio- and stereoselectivity origin.

Zinc(II)-mediated nitrile-amidoxime coupling gives new insights into H⁺-assisted generation of 1,2,4-oxadiazoles.

The cyanamides Me2NCN (1a), OC4H8NCN (1b), and PhC(═O)N(H)CN (1c) and the conventional nitriles PhCN (1d) and EtCN (1e) react with 1 equiv of each of the amidoximes R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) in the presence of 1 equiv of ZnCl2 producing the complexes [ZnCl2{HN═C(R)ON═C(R')NH2}] (R/R' = NMe2/Me (3a), NMe2/Ph (3b), NC4H8O/Me (3c), NC4H8O/Ph (3d), N(H)C(═O)Ph/Me (3e), N(H)C(═O)Ph/Ph (3f), Ph/Me (3g), Ph/Ph (3h), Et/Ph (3j)) with the chelate ligands originating from the previously unreported zinc(II)-mediated nitrile-amidoxime coupling. Addition of 1 equiv of p-TolSO3H to any of one 3a-h, 3j results in the ligand liberation and formation of the iminium salts [H2N═C(R)ON═C(R')NH2](p-TolSO3) ([4a-j](p-TolSO3)), which then at 20-65 °C spontaneously transform to 1,2,4-oxadiazoles (5a-j). As a side reaction, cyanamide derived species [4a-f](p-TolSO3) undergo Tiemann rearrangement to produce the substituted ureas R'NHC(═O)NH2 (R' = Me (6a), Ph (6b)) and RC(═O)NH2 (R = NMe2 (6c), NC4H8O (6d), N(H)C(═O)Ph (6e)), whereas phenyl and ethyl cyanide derivatives besides their transformation to the oxadiazoles undergo hydrolysis to the parent amidoxime R'C(═NOH)NH2 (R' = Me (2a), Ph (2b)) and the carboxamides RC(═O)NH2 (R = Ph (6f), Et (6g)). All new obtained compounds were characterized by HRESI-MS, IR, ATR-FTIR, (1)H NMR, CP-MAS TOSS (13)C NMR, elemental analyses (C, H, N), and single crystal X-ray diffraction for seven species (3a-e, [4b](p-TolSO3), and [4d](p-TolSO3)). Two previously unknown heterocycles 5c and 5e were isolated and characterized by elemental analyses (C, H, N), HRESI-MS, IR, (1)H and (13)C{(1)H} NMR. The observed conversion of [4a-j](p-TolSO3) to the 1,2,4-oxadiazoles uncovers the mechanism of the previously reported H(+)-assisted generation of these heterocycles (Augustine; et al. J. Org. Chem. 2009, 74, 5640).

Technetium and rhenium pentacarbonyl complexes with C2 and C11 ω-isocyanocarboxylic acid esters.

Technetium(I) and rhenium(I) pentacarbonyl complexes with ethyl 2-isocyanoacetate and methyl 11-isocyanoundecanoate, [M(CO)5(CNCH2COOEt)]ClO4 (M = Tc (1) and Re (2)) and [M(CO)5(CN(CH2)10COOMe)]ClO4 (M = Tc (3) and Re (4)), were prepared and characterized by IR, (1)H NMR, and (13)C{(1)H} NMR spectroscopy. The crystal structures of 1 and 2 were determined using single-crystal X-ray diffraction. The kinetics of thermal decarbonylation of technetium complexes 1 and 3 in ethylene glycol was studied by IR spectroscopy. The rate constants and activation parameters of this reaction were determined and compared with those for [Tc(CO)6](+). It was found that rhenium complexes 2 and 4 were stable with respect to thermal decarbonylation. Histidine challenge reaction of complexes 1 and 2 in phosphate buffer was examined by IR spectroscopy. In the presence of histidine, the rhenium pentacarbonyl isocyanide complex partially decomposes to form an unidentified yellow precipitate. Technetium analogue 1 is more stable under these conditions.

Synthesis, characterization and pre-clinical evaluation of (99m) Tc-tricarbonyl complexes as potential myocardial perfusion imaging agents.

Myocardial perfusion imaging is an established Nuclear Medicine investigation. Current myocardial perfusion imaging agents sestamibi and tetrofosmin have number of drawbacks; low heart uptake coupled with uptake into the surrounding tissues leads to a poorer image quality. There is a need for continued research into designing and evaluating potentially superior myocardial imaging agents. Tri-carbonyl-technetium and rhenium complexes were prepared by combination with mono-dentate and bi-dentate ligands. Complexes were characterized by HPLC, MAS, nuclear magnetic resonance, infrared, single-crystal X-ray diffraction and partition coefficient determinations. (99m) Tc(CO)3 complexes were administered intravenously to Sprague Dawley rats, and tissue distribution studies were carried out at 15 min and 1 h p.i. Radiochemical purity was assessed as >90%. 1-10-phenanthroline, 2,2'-bipyridine and imidazole complexes gave the highest heart uptake. The percentage injected dose per gram (n = 3) at 1 h for 1-10-phenanthroline/imidazole was blood 0.21 ± 0.01, heart 1.12 ± 0.11, kidney 3.61 ± 1.13, liver 0.62 ± 0.06, lung 0.28 ± 0.12, spleen 0.24 ± 0.05, small intestine contents 1.87 ± 0.92; and for 2,2'-bipyridine /imidazole was blood 0.23 ± 0.02, heart 1.07 ± 0.18, kidney 3.31 ± 1.28, liver 0.56 ± 0.09, lung 0.14 ± 0.02, spleen 0.2 ± 0.1, small intestine content 1.05 ± 0.48. Further investigation to evaluate more complexes based on 1,10-phenanthroline, 2,2'-bipyridine and imidazole derivatives could potentially lead to agents with an increased heart uptake and faster clearance from the liver and gastrointestinal tract.

Dichloridobis[3-(4-chloro-phen-yl)-2,N,N-trimethyl-2,3-di-hydro-1,2,4-oxa-diazole-5-amine-κN (4)]platinum(II)-4-chloro-benzaldehyde (1/1).

In the title 1:1 co-crystal, [PtCl2(C11H14ClN3O)2]·C7H5ClO, the coordination polyhedron of the Pt(II) atom is slightly distorted square-planar with the chloride and 2,3-di-hydro-1,2,4-oxa-diazole ligands mutually trans, as the Pt atom lies on an inversion center. The 4-chloro-benzaldehyde mol-ecules are statistically disordered about an inversion centre with equal occupancies for the two positions. The Pt(II) complex forms a three-dimensional structure through C-H⋯Cl and weaker C-H⋯O inter-actions with the 4-chloro-benzaldehyde mol-ecule.

Evolution of Chernobyl Corium in Water: Formation of Secondary Uranyl Phases.

Two crystalline phases, which are analogues of common secondary uranyl minerals, namely, becquerelite (Ca[(UO2)6O4 (OH)6]·8H2O) and phurcalite (Ca2[(UO2)3O2 (PO4)2]·7H2O) were identified on the surface of a Chernobyl corium-containing sample affected by hydrothermal alteration in distilled water at 150 °C for one year. Phases were characterized using Single-Crystal X-ray Diffraction Analysis (SCXRD) as well as optical and scanning electron microscopy. Features of the structural architecture of novel phases, which come from the specific chemical composition of the initial fragment of Chernobyl sample, are reported and discussed. Precise identification of these phases is important for modelling of severe nuclear accidents and their long-term consequences, including expected corium-water interaction processes at three damaged Units of the Nuclear Power Plant Fukushima Daiichi.