Slow reductive elimination from arylpalladium parent amido complexes.
We report reductive eliminations of primary arylamines from a series of bisphosphine-ligated arylpalladium(II) parent amido complexes that counter several established trends. In contrast to arylamido and alkylamido complexes of the aromatic bisphosphines DPPF and BINAP, parent amido complexes of these ligands do not form or undergo reductive elimination of monoarylamines. However, arylpalladium parent amido complexes ligated by the alkylbisphosphine CyPF-t-Bu do form in good yield and undergo reductive elimination. Despite the basicity of the parent amido ligand and the typically faster reductive elimination from complexes containing more basic amido ligands, the CyPF-t-Bu-ligated arylpalladium parent amido complexes undergo reductive elimination much more slowly than the analogous complexes containing arylamido or alkylamido ligands. Moreover, the parent amido complexes form more rapidly and are more stable thermodynamically in a series of exchange processes than the arylamido complexes. Computational studies support the overriding influence of steric effects on the stability and reactivity of the parent amido complex. The slow rate of reductive elimination causes the arylpalladium amido complex to be the resting state of the coupling of aryl halides with ammonia catalyzed by CyPF-t-Bu-ligated palladium, and this resting state contrasts the Pd(0) or arylpalladium(II) resting states of reactions of aryl halides with amines catalyzed by most palladium complexes.
Klinkenberg
Jessica L
JL
Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Hartwig
John F
JF
D000577:Amides / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D013237:Stereoisomerism
D000577:Amides; D000588:Amines; D009942:Organometallic Compounds; D010720:Phosphines; D010165:Palladium