RESUMO
Reaction of [Bu(4)N](2)[Pd(2)Br(6)(Se(2)N(2))] with [14]aneS(4) results in eventual formation of Se(4)N(4); intermediates in this reaction include an air-sensitive insoluble material which reacts with [PtCl(2)(PMe(2)Ph)](2) to give the first example of a platinum adduct of Se(2)N(2) and with [Pd(2)Br(6)](2-) to regenerate the starting material.
RESUMO
The reaction of (Me3SiNSN)2S with TeCl4 in CH2Cl2 affords Cl2TeS2N2 (1) and that of (Me3SiNSN)2Se with TeCl4 produces Cl2TeSeSN2 (2) in good yields. The products were characterized by X-ray crystallography, as well as by NMR and vibrational spectroscopy and EI mass spectrometry. The Raman spectra were assigned by utilizing DFT molecular orbital calculations. The pathway of the formation of five-membered Cl2TeESN2 rings by the reactions of (Me3SiNSN)2E with TeCl4 (E = S, Se) is discussed. The reaction of (Me3SiNSN)2Se with [PPh4]2[Pd2X6] yields [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, 4a; Br, 4b), the first examples of complexes of the (Se2N2S)2- ligand. In both cases, this ligand bridges the two palladium centers through the selenium atoms.
RESUMO
The reaction of Se(4)N(4) with (Bu(4)N)(2)[Pd(2)Br(6)] gives the title compound, (C(16)H(36)N)(2)[Pd(2)Br(6)(N(2)Se(2))], in good yield. The [Pd(2)(Se(2)N(2))Br(6)](2-) anion lies on an inversion centre, and therefore the asymmetric unit contains half a formula unit. The crystal structure confirms the coordination of the Se(2)N(2) unit to Pd through the N atoms, as previously assigned by IR spectroscopic analysis [Kelly, Slawin & Soriano-Rama (1997). J. Chem. Soc. Dalton Trans. pp. 559-562]. The title compound contains the longest Pd-N bond so far observed for such systems.
