Optically active cyclopalladated derivatives of arylimines. Crystal structures of (+)-[{Pd[p-MeOC6H3CHNCH2-(1S,2R,5S)CHCH2CH2CHC(Me)2CHCH2](μ-X)}2] (X = Cl or Br), (+)-[Pd{p-MeOC6H3CHNCH2-(1S,2R,5S )-CHCH2CH2CHC(Me)2CHCH2}Cl(PPh3)] and (+)-[{Pd[p-MeOC6H3CHNCH2-(1S,2R,5S)-CHCH2CH2CHC(Me)2CHCH2]Cl}2{Fe(δ5-C5H4PPh2)2}]

Cyclometalated Palladium(II) Fragments as Building Blocks in the Construction of New Heteronuclear Metalomacrocycles

“…The Pd−N bond lengths Pd(1)−N(1‘), 2.120(5) Å, and Pd(2)−N(2‘), 2.127(6) Å, are longer than the expected value of 2.01 Å calculated from the covalent radii of N(sp 2 ) and palladium (0.70 and 1.31 Å, respectively), reflecting the strong trans influence of the phosphine ligand. The Pd−P and Pd−C bond lengths are shorter than the values predicted from their covalent radii, consistent with those found in related complexes. − The terminal palladium−bromine bonds [Pd(1)−Br(1), 2.4971(8) Å; Pd(2)−Br(2), 2.5137(9) Å] are somewhat longer than the sum of their covalent radii, revealing the strong trans influence of the C(phenyl) atom. , The two cyclometalated rings containing the Pd(1) atom and its symmetry equivalent Pd(1‘) atom are planar (rms 0.0056 Å) and approximately coplanar (4.9°) with the aromatic phenyl ring of the Schiff base (rms 0.0184 Å). However, in the case of the Pd(2), Pd(2‘) moiety the angle between the metalated aromatic ring (rms 0.0542 Å) and the cyclometalated rings (rms 0.0646 Å) is rather large, 10°, most probably due to structural requirements in the complex.…”