Abstract
Abstract Reductive dehalogenation of BiCl3 with Na2W2(CO)10 leads to Bi2[W(CO)5]3 (1), which contains an axial Bi2 ligand side-on coordinated to three W(CO)5 groups. The star-type arrangement of three metal carbonyl moieties around a Bi2 axis with a very short Bi-Bi bond distance (281.8(3) pm) and a Bi2W3 core of approximate D3h symmetry is proved by an X-ray analysis (R1 = 0.041). 1 is thus the highest homologue of a series of complexes X2[W(CO)5]3 (X = As, Sb, Bi) and is the first stable molecular compound to contain a Bi2 ligand.
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