Abstract
The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as iPrDPDBFphos) was prepared and studied for its potential as a trans-chelating ligand in transition-metal coordination complexes. In the rhodium norbornadiene complex [(iPrDPDBFphos) Rh(NBD)]BF4, which has been characterized with multinuclear NMR spectroscopy, X-ray crystallography, and electrochemical studies, the ligand binds in cis fashion. In the bis(acetonitrile) complexes of rhodium and palladium [(iPrDPDBFphos)M(CH3CN)2](BF 4)n (M = Rh, Pd; n = 1, 2), the ligand adopts a trans coordination geometry. Density functional theory (DFT, M06-L) calculations predict that the trans conformer is energetically more favorable than the cis by 3.5 kcal/mol. Cyclic voltammograms of the bis(acetonitrile) Pd(II) and Rh(I) complexes contain reversible and quasi-reversible reduction events, respectively, which are preliminarily assigned as metal-based redox reactions.
Original language | English (US) |
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Pages (from-to) | 2545-2552 |
Number of pages | 8 |
Journal | Inorganic chemistry |
Volume | 50 |
Issue number | 6 |
DOIs | |
State | Published - Mar 21 2011 |