Reactions of di(2-pyridyl) ketone, (py) 2 CO, with indium-(III) halides in CH 3 NO 2 have been studied, and a new transformation of the ligand has been revealed. In the presence of In III , the CO bond of (py) 2 CO is subjected to nucleophilic attack by the carbanion − :CH 2 NO 2 , yielding the dinuclear complexes [In 2 X 4 {(py) 2 C(CH 2 NO 2 )(O)} 2 ] (X = Cl, 1; X = Br, 2; X = I, 3) in moderate to good yields. The alkoxo oxygens of the two η 1 :η 2 :η 1 -(py) 2 C(CH 2 NO 2 )(O) − ligands doubly bridge the In III centers and create a {In 2 (μ 2 -OR) 2 } 4+ core. Two pyridyl nitrogens of different organic ligands and two terminal halogeno ions complete a distorted-octahedral stereochemistry around each In(III) ion. After maximum excitation at 360 or 380 nm, the solid chloro complex 1 emits blue light at 420 and 440 nm at room temperature, the emission being attributed to charge transfer within the coordinated organic ligand. Solidstate 115 In NMR spectra, in combination with DFT calculations, of 1−3 have been studied in detail at both 9.4 and 14.1 T magnetic fields. The nuclear quadrupolar and chemical shift parameters provide valuable findings concerning the electric field gradients and magnetic shielding at the nuclei of indium, respectively. The experimentally derived C Q values are 40 ± 3 MHz for 1, 46 ± 5 MHz for 2, and 50 ± 10 and 64 ± 7 MHz for the two crystallographically independent In III sites for 3, while the δ iso values fall in the range 130 ± 30 to −290 ± 60 ppm. The calculated C Q and asymmetry parameter (η Q ) values are fully consistent with the experimental values for 1 and 2 and are in fairly good agreement for 3. The results have been analyzed and discussed in terms of the known (1, 3) and proposed (2) structural features of the complexes, demonstrating that 115 In NMR is an effective solid-state technique for the study of indium(III) complexes.

Reactions of 2-benzoylpyridine, (py)(ph)CO, with InX3 (X = Cl, Br) in EtOH at room temperature have been studied. The InCl3/(py)(ph)CO system has provided access to complex [InCl3{(py)(ph)CO}(EtOH)]∙{(py)(ph)CO} (1) and the...

The coordination ability of As(III) thiolates, having two kinds of Lewis base atoms [As(III) and S(II)], towards heavy metal salts was virtually not studied. We have found that As(SPh)3 (A), Me-As(SPh)2 (B), and 2-O2N-PhS-As(SPh)2 (C) with the acetates M(OAc)2 (M = Cd, Pb, Hg) gave the metal thiophenolate M(SPh)2 (except in the case of B and Cd(OAc)2 which gave PhS-Cd-OAc·Cd(SPh)2) and with HgCl2 gave (PhS-Hg-Cl)2·HgCl2. The thiophenolates of cadmium and lead(II) were not reactive towards their corresponding acetates and chlorides, while Hg(SPh)2 gave PhS-Hg-OAc and (PhS-Hg-Cl)2·HgCl2. Likely mechanisms for these reactions are suggested.