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Reactions of a series of unsymmetrically substituted N-heterocyclic carbene ligands with Ru3(CO)12afforded a variety of mononuclear (1, 2), trinuclear (3, 4, 5, and 5′), and tetranuclear (6, 7) ruthenium complexes via intramolecular ruthenium-mediated sp2and sp3C–H bond activations. Complexes 6and 7include an octahedral cluster skeleton consisting of four ruthenium atoms and two metalated carbon atoms. The formation of this type of ruthenium clusters is proposed to involve the initial C–C double-bond migration and subsequent sp2C–H bond activations. All new complexes were fully characterized, and the molecular structures of 1, 2, 5, 6, and 7were determined by X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Six cadmium(II) complexes containing the N2O2donor tetradentate asymmetrical Schiff base ligand 2-{[2-(dimethylamino)ethylimino]methyl}-6-methoxyphenol (HL5), namely, [(Cd3L52Cl4)2]·CH3OH·H2O (1), [Cd(L5)Cl]2·CH3OH (2), [Cd2(HL5)Cl4]n(3), {[Cd3(H2L5)2Cl8]·2H2O}n(4), [(H2L5)2]2·[CdCl4]2−·H2O (5), and [(H2L5)2]2·[CdCl4]2−(6), have been synthesized using cadmium(II) chloride and the asymmetrical Schiff base ligand HL5under different pH conditions at room temperature. The diverse structures show the marked sensitivity of the structural chemistry of the tetradentate asymmetrical Schiff base ligand HL5. Complex 1formed at pH = 10 exhibits a rare zero-dimensional structure of trinuclear cadmium(II). At pH = 8−9, a dinuclear cadmium(II) complex 2is formed. The reaction at pH = 5−7 leads to two one-dimensional structures of 3and 4. A further decrease of the pH to 3−5 results in a zero-dimensional structure 5. Owing to the departure of lattice water molecules in the crystal, complex 5at room temperature can gradually undergo single-crystal-to-single-crystal transformation to result in complex 6.The results further show that conversions of complex 1−5can also be achieved by adjusting the pH value of the reaction solution, 1→ 2pH=8→ 5pH=3and 3→ 4pH=5. Comparing these experimental results, it is clear that the pH plays a crucial role in the formation of the resulting structures, which simultaneously provides very effective strategies for constructing the CdIIcompounds with N2O2donor tetradentate asymmetrical Schiff base ligand. The strong fluorescent emissions of the six compounds (1−6) make them potentially useful photoactive materials. Furthermore, six Schiff base cadmium complexes (1−6), with 2,2-dipheny1-1-picrylhydrazy1 (DPPH) as a co-oxidant exhibited the stronger scavenging activity. [ABSTRACT FROM AUTHOR]

A series of molybdenum/tungsten polyoxometalate compounds, namely, [(MII(HL)2)Mo3O10] (M = Mn (1), Co (2), Ni (3)), [CuII2(L)2(HL)2]2(Mo8O26) (4), [Zn(HL)2(MoO4)]2·HL·4H2O (5), [CuII4(L)6WO4)]·3H2O (6) (HL = 3-(2-pyridyl)pyrazole), were designed and synthesized under hydrothermal conditions. X-ray diffraction analyses reveal that compounds 1−3have an isostructural wavelike chain structure consisting of the asymmetric building blocks of [Mo3O10], in which the ratio of octahedron {MoO6} and square pyramid {MoO5} is 1:2. The hexacoordinated transitional metal cation, just like one “anchor” to fix the above wavelike chain, is linked by two terminal oxygen atoms belonging to two edged asymmetric molybdate [Mo3O10]2−units, and further chelated by two 3-(2-pyridyl)pyrazole ligands. Although a similar synthetic method in preparation of 1−5was employed, compounds 4and 5show a completely different structure compared to compounds 1−3. Compound 4is composed of two separate parts of the [CuII2(L)2(HL)2]2+dimer and the ε-[Mo8O26]4−unit. Compound 5consists of a bimetallic tetranuclear cluster that is constructed from corner-sharing {MoO4} tetrahedra and {ZnN4O2} distorted octahedron forming a cyclic {Zn2Mo2O4} core. For compound 6, a one-dimensional structure is composed of WO42−linked by the centrosymmetric tetranuclear copper grids, in which two approximately planar [CuII(L)]2units with an inversion center stack parallel and face-to-face linked by two additional deprotonated ligands of L−1perpendicularly. [ABSTRACT FROM AUTHOR]

In the title complex, (C8H20N)2[Cu(C3S5)2], each Cu atom is tetracoordinated by four dmit S atoms (dmit is 2-thio­xo-1,3-di­thiole-4,5-di­thiol­ate), forming a slightly distorted square-planar arrangement. The average Cu—S bond length is a little larger than the sum of the single-bond covalent radii. The S—Cu—S bond angles for the vicinal S atoms are somewhat larger than the typical right angle and the other two angles are much smaller than 180°. The [Cu(dmit)2]2− anions and tetraethyl­ammonium counter-cations form a layered arrangement in the crystal structure. [ABSTRACT FROM AUTHOR]