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Angew Chem Int Ed Engl. 2016 Aug 1;55(32):9253-8. doi: 10.1002/anie.201604903. Epub 2016 Jun 27.

Monomeric Chini-Type Triplatinum Clusters Featuring Dianionic and Radical-Anionic π*-Systems.

Author information

1
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA.
2
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA. jsfig@ucsd.edu.

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.

KEYWORDS:

cluster compounds; isocyanides; non-innocent ligands; platinum

PMID:
27346691
DOI:
10.1002/anie.201604903

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