Abnormal-NHC Palladium(II) Complexes: Rational Synthesis, Structural Elucidation, and Catalytic Activity

Reaction of a C2-arylated imidazolium iodide (IPrPh)I (1) (IPrPh = 1,3-bis(2,6-diisopropylphenyl)-2-phenyl-imidazolium) with PdCl2 in the presence of Ag2O affords abnormal N-heterocyclic carbene (aNHC) palladium complexes (aIPrPh)PdCl2 (2) and (aIPrPh)2PdCl2 (3) (aIPrPh = 1,3-bis(2,6-diisopropylphenyl)-2-phenyl-imidazol-4-ylidene). Treatment of 2 with a pyridine gives Pd-PEPPSI-type complexes (aIPrPh)PdCl2(L) (L = pyridine (py), 5; L = 3-chloropyridine (3Cl-py), 6). Compounds 5 and 6 are also accessible by a one-pot reaction of 1, PdCl2, and Ag2O in a pyridine solvent. While the use of a conventional base K2CO3 leads to the formation of mixed halide complexes (aIPrPh)Pd(Cl)I(L) (7, L = py; 8, L = 3Cl-py), iodide derivatives (aIPrPh)PdI2(L) (9, L = py; 10, L = 3Cl-py) can be selectively prepared with addition of an excess of KI to the reaction mixture. Albeit in a low yield, a putative transmetalation agent {(aIPrPh)2Ag}AgI2 (4) has been isolated and characterized. Compounds 2–10 are air stable crystalline...