The 14e- Pd(0)L2 complex 2 was prepared by reduction of [Pd(2-methylallyl)Cl]2 in the presence of the new, electron-rich, bulky methoxy benzyl phosphine (dmobp) ligand 1. Structural characterization of this complex indicates that the methoxy groups are not coordinated to the metal center. Complex 2 undergoes oxidative addition of iodo- and chlorobenzene at room temperature to yield the monophosphine complexes LPd(Ph)X (4, X = I; 5, X = Cl) in which the methoxy group is coordinated to the Pd(II) center in the solid state, as indicated by the X-ray structure of 4. In solution there is no evidence for methoxy coordination, indicating the availability of a Pd(II) 14e- complex. The Me−O bond in 4 is longer than the corresponding bond in 2, indicating that coordination of the methoxy group weakens the C−O bond. Reaction of complex 4 or 5 with the free ligand 1 results in nucleophilic attack and C−O cleavage, leading to the dimeric phenoxy-bridged complex 7, which was structurally characterized. Partial reductio...