No abstract

In this work, ortho-palladated complexes [Pd(µ-Cl)(C 6 H 4 CH 2 NRR -κ 2 -C,N)] 2 and [Pd(C 6 H 4 CH 2 NH 2 -2-C,N)Cl(Y)] were tested in the Suzuki-Miyaura cross-coupling reaction. Cyclopalladated Pd(II) complexes as thermally stable catalysts can activate aryl bromides and chlorides. These complexes were active and efficient catalysts for the Suzuki-Miyaura reaction of aryl bromides and even less reactive aryl chlorides. The cross-coupled products of a variety of aryl bromides and aryl chloride with phenylboronic acid in methanol as solvent at 60• C were produced in excellent yields.

The ortho-metalated complex [Pd(x){j 2 (C,N)-[C 6 H 4 CH 2 NRR 0 (Y)}] (2a-4a and 2b-3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc) 2 and secondary benzylamine [a, EtNHCH 2 Ph; b, t-BuN-HCH 2 Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){j 2 (C,N)-[C 6 H 4 CH 2 NRR 0 (Y)}] (2a-4a and 2b-3b) with a stoichiometric amount of Ph 3 P=C(H)COC 6 H 4 -4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C 6 H 4 C=CHPPh 3 ){j 2 (C,N)-[C 6 H 4 -CH 2 NRR 0 (Y)}] (5a-9a, 4b-6b, and 4b 0 -6b 0 ), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an ''end-on carbonyl''. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a-9a, 4b-6b, and 4b 0 -6b 0 ) were characterized by elemental analysis as well as various spectroscopic techniques.

In the cation of the title compound, C32H26OP+·CF3O3S−, the dihedral angle between the benzene rings of the biphenyl group is 42.37 (8)°. In the crystal, the cations and anions inter­act through inter­molecular C—H⋯O hydrogen bonds, forming chains parallel to the b axis. These chains are further linked by C—H⋯π stacking inter­actions into layers parallel to the bc plane.