Chemical transformations supported by the [Re 63- Se) 8] 2+ cluster core

Research output: Contribution to journalReview article

10 Scopus citations

Abstract

This Perspective article discusses three interesting chemical transformations promoted by the octahedral [Re 63-Se) 8] 2+ cluster core. These include (1) nucleophilic addition of alcohols to cluster-bound nitrile(s) to produce imino ester complexes; (2) synthesis of cluster-imine complexes with geometric specificity by reacting cluster nitrile solvates with organic azides; and (3) preparation and reactivity studies of carbonyl complexes of the cluster. We found that cluster-bound nitrile ligands were activated toward nucleophilic attack by methanol or ethanol, affording predominantly the Z-configured cluster-imino ester complexes, for which a mechanism evoking bifurcated hydrogen bonding interactions involving both the alcohol OH group and two nearest Se atoms of the cluster core was proposed. When reacted with organic azides, cluster-bound nitrile ligands were displaced and cluster-imine complexes were obtained, presumably through the formation of the corresponding cluster-azide complexes, followed by their photodecomposition. Lastly, cluster complexes featuring all-terminal carbonyl ligands were synthesized. Back-bonding interactions were verified, both experimentally and by computational studies. Their thermal and photo-stabilities were also evaluated, so was their reactivity toward methyl lithium for the eventual making of cluster-carbene catalysts. These findings, together with those by others, portend an exciting, new direction in the chemistry of solid-state type transition metal clusters.

Original languageEnglish (US)
Pages (from-to)5121-5131
Number of pages11
JournalDalton Transactions
Volume41
Issue number17
DOIs
StatePublished - May 7 2012

    Fingerprint

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this