Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems |
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| Authors: | Brandon R Barnett Prof Arnold L Rheingold Prof Joshua S Figueroa |
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| Institution: | Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA, USA |
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| Abstract: | Owing to their unique topologies and abilities to self‐assemble into a variety of extended and aggregated structures, the binary platinum carbonyl clusters Pt3(CO)6]n2? (“Chini clusters”) continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron‐transfer series Pt3(μ‐CO)3(CNArDipp2)3]n? (n=0, 1, 2), which represents a unique set of monomeric Pt3 clusters supported by π‐acidic ligands. Spectroscopic, computational, and synthetic investigations demonstrate that the highest‐occupied molecular orbitals of the mono‐ and dianionic clusters consist of a combined π*‐framework of the CO and CNArDipp2 ligands, with negligible Pt character. Accordingly, this study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in a redox non‐innocent manner. |
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| Keywords: | cluster compounds isocyanides non-innocent ligands platinum |
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