Abstract

Reactions between tungsten halides are discussed along the series of compounds WCl6 → WCl4 → W6Cl12 ↔ W6Cl18 → [W6CCl18]n− ← [W3Cl13]u−, focusing on the two closely related tungsten chloride compounds whose structures compromise the well-known octahedro W6Cl18 cluster and the carbon-centered triprismo W6CCl18 cluster. Both clusters can be regarded as being built by merging two trigonal [W3Cl13]u− units in different ways. Syntheses, structural transformation reactions, and concepts regarding electronic structures are reported.

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