- Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II)
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Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2′-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) cation-cation interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with complex 4, crystallizes as a 2D network as a result of the high degree of connectivity provided by the chelating/bridging tricarboxylate ligand. Emission spectra measured in the solid state display vibronic fine structure attributable to uranyl luminescence (except for complex 5, in which emission is quenched), with variations in maxima positions associated with modifications of the uranyl ion environment.
- Thuéry, Pierre,Harrowfield, Jack
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p. 6799 - 6816
(2016/07/16)
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- Production method of a cross-coupling compound from an alkyl halide and an organoboron compound
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There is provided a method for producing a coupling compound of formula (1):(Y-)(n-1)R1-R2-(R1)(n'-1) wherein R1, R2 n and n' are as defined below, Y is R2 or X as defined below, which method comprises reactinganorganichalogen compound of formula (2):n' (R1X1n) wherein X1 represents a bromine or iodine, R1 represents a substituted or unsubstituted, linear, branched or cyclic hydrocarbon group of which α and β carbon atoms in relation to X1 are sp3 carbon atoms, n and n' each independently represent an integer of 1 or 2, and provided that n and n' do not simultaneously represent 2, with an organic boron compound of formula (3):m{R2(BX22)n'} wherein R2 represents a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted alkenyl group and the boron atom is bonded with an sp2 carbon atom thereof, X2 represents a hydroxyl or alkoxy group, n' is as defined above, m represents an integer of 1 or 2, and m is not more than n, in the presence of a catalyst comprising a) a nickel compound, and ???b) b-1) a compound of formula (i): ???or ???b-2) a compound of formula (ii):
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