Abstract
Organometallic Pd(III) complexes have been implicated as intermediates in a number of catalytic and stoichiometric transformations. While a few dinuclear organometallic Pd(III) complexes have been characterized, no mononuclear organometallic Pd(III) complexes have been isolated to date. Reported herein is the synthesis and characterization of a series of Pd(III) complexes supported by the tetradentate ligand N,N′-di-tert-butyl-2,11-diaza[3.3](2,6) pyridinophane (N4). Chemical or electrochemical oxidation of the Pd(II) complexes (N4)PdII(R)(X) (R = Me, X = Cl: 1; R = Ph, X = Cl: 2; R = X = Me: 3) generates [(N4)PdIIIMeCl]+ (1+), [(N4)PdIIIPhCl]+ (2+), and [(N4)Pd IIIMe2]+ (3+). These stable Pd(III) complexes were isolated and characterized by X-ray diffraction, cyclic voltammetry, UV-vis, EPR, magnetic moment measurements, and DFT to confirm the presence of paramagnetic d7 Pd(III) centers. Moreover, these Pd(III) complexes undergo light-induced C-C bond formation to give the corresponding homocoupled products ethane or biphenyl. Particularly remarkable is the observation for the first time of ethane formation from monomethyl Pd complexes.
Original language | English (US) |
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Pages (from-to) | 7303-7305 |
Number of pages | 3 |
Journal | Journal of the American Chemical Society |
Volume | 132 |
Issue number | 21 |
DOIs | |
State | Published - Jun 2 2010 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry