Abstract
Reactions of the trinuclear Lewis acid perfluoro-ortho-phenylene) mercury [(o-HgC6F4)3] (1) with the polypnictogen complex [CpMo(CO)(2)(eta(3)-P-3)] (2) containing a cyclo-P-3 ligand and the series of E-2 complexes [{CpMo(CO)(2)}(2)(mu, eta(2):eta(2)-E-2)] (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 ...
Abstract
Reactions of the trinuclear Lewis acid perfluoro-ortho-phenylene) mercury [(o-HgC6F4)3] (1) with the polypnictogen complex [CpMo(CO)(2)(eta(3)-P-3)] (2) containing a cyclo-P-3 ligand and the series of E-2 complexes [{CpMo(CO)(2)}(2)(mu, eta(2):eta(2)-E-2)] (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 center dot center dot center dot E contacts below the respective sum of the van der Waals radii. The complexes 2 (P-3), 3a (P-2) and 3b (As-2) show interactions of only one pnictogen atom with all three Hg atoms of 1. The complex 3c (Sb-2) 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 Bi-2 complex 3d shows an almost parallel alignment of the Bi-2 dumbbell situated above the center of the planar Lewis acid 1. The arrangements of the E-2 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 Sb-2 complex 3c, the Bi-2 complex 3d, the starting material of its preparation [Bi{CpMo(CO)(3)}(3)] (4) and an unprecedented 'Cr4As5' cluster 5 are presented.
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