Treatment of the intramolecular eta2-arene complexes Pd[C7H8(eta2-Ar)](PPh3)I, where Ar = CrH5, p-CH3Cr6H4, and p-CH3OC6H4, in dichloromethane with aqueous sodium hydroxide in the presence of PPh3 led to isolation of the corresponding yellow ortho-metalation products Pd[C7H8(C6H3R)](PPh3)2 (R = H (2a), p-CH3 (2b), and p-OCH3 (2c)). 2a reacts with CH3I to give the o-methyl product Pd[C7H8(C6H4-o-CH3)](PPh3)I (1d) and with HC1, HC=CPh, CH30COC=CCOOCH3, and (NC)2C=C(CN)2 to afford the substituted nortricyclene C7H9Ph (4a), the exo-disubstituted norbornene derivative C7H8(C=CC6H5) (CrH5) (5a), the insertion product C7H8[Cr6H4(C(COOCH3)=CCOOCH3)] (6a), and the benzocyclobutane product C7H8(CrH4) (8a), respectively.