Host–guest interactions of the cluster [triangulo-Hg3(μ-dppm)3]4+ (dppm=bis(diphenylphosphino)methane) with halides and pseudohalides
2000; Elsevier BV; Volume: 19; Issue: 7 Linguagem: Inglês
10.1016/s0277-5387(00)00335-1
ISSN1873-3719
AutoresB. Scheffter, Walter Schuh, K.‐H. Ongania, Holger Kopacka, R. Malleier, Klaus Wurst, Paul Péringer,
Tópico(s)Radioactive element chemistry and processing
ResumoThe complexes [triangulo-Hg3(μ-dppm)3Xn](4−n)+ (X=Cl, Br and I, n=1, 2) are formed in a small extent upon addition of halides to the cationic subvalent cluster [triangulo-Hg3(μ-dppm)3]4+, whereas SeCN− and CN− cause quantitative fragmentation. The cluster [triangulo-Hg3(μ-dppm)3(SCN)2]2+ is produced either by the reaction of [triangulo-Hg3(μ-dppm)3]4+ with thiocyanate or via reduction of a mixture of Hg(SCN)2, [Hg(Me2SO)6](O3SCF3)2 and 3 mequiv. of dppm with elemental mercury. The X-ray structure of [Hg3(μ-dppm)3(SCN)2](O3SCF3)2 shows a Hg3 triangle (Hg–Hg distances 286.60(14), 279.32(12) and 281.2(2) pm) spanned by three dppm ligands. The thiocyanate ions are positioned nearly parallel to the Hg3 plane in the two cavities formed by the Hg3 group at the bottom and the phenyl groups of the dppm ligands as the walls (Hg1–S1 277.5(6) and Hg3–S2 278.4(6) pm). Phosphorus-31 solution NMR indicates a rapid rotation of the SCN− ligands about the Hg3 triangle within the cavity.
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