The compound Pd(η 3 -1-Ph-C 3 H 4 )(η 5 -C 5 H 5 ) (I) reacts cleanly with many tertiary phosphines L to undergo reductive elimination of PhC 3 H 4 -C 5 H 5 and form palladium(0) species of the types PdL n (n = 2, 3), long believed to be exemplary catalysts for Suzuki−Miyaura, Heck−Mizoroki, and Sonogashira cross-coupling reactions. I has accordingly been shown to be generally much more effective for these catalytic processes than are conventional catalyst precursors such as Pd(PPh 3 ) 4 , Pd 2 (dba) 3 , PdCl 2 , and Pd(OAc) 2 , in large part because I stands alone in this series for its ability to generate specifically and efficiently the desired species PdL 2 in many cases. We have now investigated I as a precursor for prototypical Buchwald−Hartwig amination reactions of 4-bromo-and 4-chloroanisole with morpholine, making comparisons with Pd 2 (dba) 3 , Pd(OAc) 2 , and [Pd(η 3 -1-Ph-C 3 H 4 )Cl] 2 (IV). In this work we have utilized PBu t 3 because of its general effectiveness, and we have also assessed XPhos and Mor-Dalphos, representatives of important classes of phosphines utilized elsewhere for amination reactions.