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Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems
Author(s) -
Barnett Brandon R.,
Rheingold Arnold L.,
Figueroa Joshua S.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201604903
Subject(s) - chemistry , monomer , isocyanide , redox , platinum , molecule , electron transfer , stereochemistry , combinatorial chemistry , crystallography , photochemistry , catalysis , organic chemistry , polymer
Owing to their unique topologies and abilities to self‐assemble into a variety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt 3 (CO) 6 ] n 2− (“Chini clusters”) continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron‐transfer series [Pt 3 (μ‐CO) 3 (CNAr Dipp2 ) 3 ] n − ( n =0, 1, 2), which represents a unique set of monomeric Pt 3 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 CNAr Dipp2 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.