Reactions of Cyclopalladated Benzylidene‐aniline Schiff 's Base Complexes. Selective Synthesis of 2′‐Substituted Schiff 's Base Derivatives and the X‐Ray Crystal Structure of the Dimer [Pd(μ‐OAc)(5′‐OCH 3 C 6 H 3 CHNC 6 H 4 ‐4‐CH 3 )] 2

The 2′‐cyclopalladated imine complex , reacts with CO in MeOH to afford the 2′‐substituted aryl imine 2′‐CO 2 CH 3 ‐5′‐OCH 3 C 6 H 3 CHNTol (Tol = C 6 H 4 ‐4‐CH 3 ). The product of this reaction can be altered by changing the bridging ligand from AcO to Cl, in which case only the 5‐membered ring heterocyclic compound is obtained. [Pd(μ‐OAc)( 1a )] 2 with 2 equiv. of Ph 3 P and CO (1 atm) gives the heterocyclic which arises from two CO insertion reactions, whereas [PdX( 1a )] 2 (X = AcO, Cl) with 4 equiv. of CNBu t and 4 equiv. of Ph 2 PCH 2 CH 2 PPh 2 affords the heterocyclic ketenimine [PdCl( 1a )] 2 reacts with CH 2 CHCO 2 CH 2 CH 3 to afford 2′(CHCHCO 2 CH 2 CH 3 )‐5′‐OCH 3 C 6 H 3 CHO, and [Pd(μ‐OAc)( 1a )] 2 with I 2 to give 2′‐I‐5′‐OCH 3 C 6 H 3 CHO. Excess CH 3 O 2 CCCCO 2 CH 3 reacts with various substituted cyclopalladated Schiff 's bases in MeOH to afford which we formulate as possessing two PdC bonds, and one coordinated ester O atom. The X‐ray crystal structure of [Pd(μ‐OAc)( 1a )] 2 has been determined; relevant bond lengths [Å] and bond angles [°] are: PdO(1), 2.139(6), PdO(2), 2.026(6), PdN, 2.039(6), PdC(2′), 1.951(8), PdPd, 3.113(1), NPdC(2′), 80.9(3), NPdO(1), 97.5(2), C(2′)PdO(2), 91.7(3), O(1)PdO(2), 89.2(2).