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Issue 35, 2016
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Supramolecular adducts based on weak interactions between the trimeric Lewis acid complex (perfluoro-ortho-phenylene)mercury and polypnictogen complexes

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Abstract

Reactions of the trinuclear Lewis acid perfluoro-ortho-phenylene)mercury [(o-HgC6F4)3] (1) with the polypnictogen complex [CpMo(CO)23-P3)] (2) containing a cyclo-P3 ligand and the series of E2 complexes [{CpMo(CO)2}2(μ,η22-E2)] (E = P(3a), As(3b), Sb(3c), Bi(3d)) are reported. In all cases, the reaction products show very weak interactions between the En ligand complexes and the Lewis acid 1, as evidenced by their highly dynamic behaviour in solution and the formation of adducts in the solid state showing Hg⋯E contacts below the respective sum of the van der Waals radii. The complexes 2 (P3), 3a (P2) and 3b (As2) show interactions of only one pnictogen atom with all three Hg atoms of 1. The complex 3c (Sb2) forms two adducts with 1 showing either a side-on coordination of the Sb2 dumbbell towards Hg or an end-on coordination of both Sb atoms towards two independent molecules of 1. The Bi2 complex 3d shows an almost parallel alignment of the Bi2 dumbbell situated above the center of the planar Lewis acid 1. The arrangements of the E2 complex series towards 1 are rationalized with the help of electrostatic potential maps obtained by DFT calculations. Finally the structural characterizations of a new modification of the free Sb2 complex 3c, the Bi2 complex 3d, the starting material of its preparation [Bi{CpMo(CO)3}3] (4) and an unprecedented ‘Cr4As5’ cluster 5 are presented.

Graphical abstract: Supramolecular adducts based on weak interactions between the trimeric Lewis acid complex (perfluoro-ortho-phenylene)mercury and polypnictogen complexes

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Publication details

The article was received on 22 Jun 2016, accepted on 18 Jul 2016 and first published on 20 Jul 2016


Article type: Paper
DOI: 10.1039/C6DT02507B
Dalton Trans., 2016,45, 13742-13749
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    Supramolecular adducts based on weak interactions between the trimeric Lewis acid complex (perfluoro-ortho-phenylene)mercury and polypnictogen complexes

    M. Fleischmann, J. S. Jones, G. Balázs, F. P. Gabbaï and M. Scheer, Dalton Trans., 2016, 45, 13742
    DOI: 10.1039/C6DT02507B

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