Main-group element-bridged transition metal carbonyl complexes represent an important field in contemporary chemistry. This review will focus on the recent development of groups 6-8 carbonyl chalcogenide clusters, in particular on the anionic clusters which have been proven to exhibit versatile reactivity. This paper presents a review and discussion, from our group and others, of the rational synthetic methodologies, structural features, cluster-growth and transformations, and novel reactivities of these anionic clusters, as well as their special electrochemical, magnetic, and semiconducting properties. The description of the clusters in this review is arranged group-by-group based on the formation of both metal-chalcogen and metal-metal bonds. The literature survey is current through January 2011, and the review covers the chemistry of anionic groups 6-8 carbonyl chalcogenide clusters in this area of research and should significantly contribute to future research.
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