title: Monomeric Chini-Type Triplatinum Clusters Featuring Dianionic and Radical-Anionic π*-Systems.
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 ]n (2-) ("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 (CNAr(Dipp2) )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 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA.
authors.forename: Brandon R
authors.initials: BR
authors.lastname: Barnett
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA.
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA. jsfig@ucsd.edu.
authors.forename: Joshua S
authors.initials: JS
authors.lastname: Figueroa
keywords: cluster compounds; isocyanides; non-innocent ligands; platinum