Artikel,

Structural variety and multiple isomerism in 1-(dimethylamino)propyl-2-chalcogenolate and 2-(dimethylamino)propyl-1-chalcogenolate complexes of palladium(II) and platinum(II): Synthesis, spectroscopy and structures

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European Journal of Inorganic Chemistry, (2004)
DOI: 10.1002/ejic.200400524

Zusammenfassung

Isomeric dichalcogenides Me2NCH(Me)CH2E2 (N$\cap$E**)2 and Me2NCH2CH(Me)E2 (N$\cap$E*)2 (E = S, Se, Te) were obtained by the reactions of NaSH or M'2E2 (M' = Na or K) with Me2NCH2CHMeCl. The former reaction affords mainly (N$\cap$E**)2 (E = S) while from the latter mixts. of (N$\cap$E**)2 and (N$\cap$E*)2 referred to as (N$\cap$E)2, E = S, Se, Te were isolated, the ratios in the mixts. depending on the chalcogen. Reactions of (N$\cap$E)Na with M2Cl2(m-Cl)2(PR3)2 gave MCl(N$\cap$E)(PR3) (M = Pd or Pt). These chiral, mixed-ligand complexes were characterized by elemental anal., IR, UV/visible and NMR (1H, 13C, 31P, 77Se, 125Te, 195Pt) spectroscopy, and, in part, by x-ray structure anal. The complexes display a typical pattern of mutually trans-oriented neutral (P and N) and anionic (Cl and E) donor atoms in an approx. square-planar environment. In contrast to the Pt(II) analogs, the x-ray structures of PdCl(N$\cap$E)(PMePh2) (E = S or Se) revealed both a conformational isomerism of the five-membered chelate ring and, for Se, the co-crystn. of complexes with both the N$\cap$E* and N$\cap$E** isomeric ligands. The thermal behavior of some complexes was studied. on SciFinder(R)

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