Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 31, Pages 10974-10983Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja9014474
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Funding
- National Science Foundation [CHE-0545909]
- Alfred P. Sloan Foundation
- Camille and Henry Dreyfus Foundation
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This paper describes the synthesis of a series of Pd-IV complexes of general structure (N similar to C)(2)Pd-IV(O2CR)(2) (N similar to C = a rigid cyclometalated ligand; O2CR = carboxylate) by reaction of (N similar to C)(2)Pd-II with Phl(O2CR)(2). The majority of these complexes undergo clean C-O bond-forming reductive elimination, and the mechanism of this process has been investigated. A variety of experiments, including Hammett plots, Eyring analysis, crossover studies, and investigations of the influence of solvent and additives, suggest that C-O bond-forming reductive elimination proceeds via initial carboxylate dissociation followed by C-O coupling from a 5-coordinate cationic Pd-IV intermediate. The mechanism of competing C-C bond-forming reductive elimination from these complexes has also been investigated and is proposed to involve direct reductive elimination from the octahedral Pd-IV centers.
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