Abstract
Reduction of a mixture containing [PtCl2(cod)], aromatic isocyanide (RNC; R = 2,6-xylyl (Xyl), 2,4,6-mesityl (Mes)), diphosphine (Ph2P(CH2)nPPh2; n = 5 (dpppn), n = 6 (dpphx)), and NH4PF6 by sodium amalgam (<1%) afforded trigonal-antiprismatic hexanuclear platinum(0) clusters encapsulating two mercury(0) atoms, [Hg2Pt6(μ-RNC)6(μ-diphos)3] (diphos = dpphx, R = Xyl (6a); diphos = dpppn, R = Xyl (8a), Mes (8b)). Complexes 6a and 8a were characterized by X-ray crystallographic analyses to demonstrate that two triangular platinum(0) units, {Pt3(μ-RNC)3}, are connected by three diphosphine ligands with long methylene chains to form a closed cage of the cluster-based metallocryptand, in which two mercury(0) atoms are incarcerated with a notably short Hg−Hg distance. In complex 8a (n = 5), the centroids of the two Pt(0) triangles are linearly arranged with respect to the Hg−Hg axis to form a pseudo-D3-symmetrical Hg2Pt6 antiprismatic cluster core (average Pt−Pt = 2.6719 A, average Pt−Hg = 2.9417 A, and Hg−Hg = 2....
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