Bis-ortho-metalated palladium complexes. New examples and reactivity. The X-ray crystal structure of cis-(2-C₆H₅N=NC₆H₄)₂Pd and cis-(2-C₆H₅N=NC₆H₄)(2-Me ₂NCH₂C₆H₄)Pd

Reaction of bis[(2-(arylazo)aryl)chloropalladium] with 2-lithio-N,N-dimethylbenzylamine yields the "mixed" ortho-metalated cis-[(2-arylazo)aryl)(2-((dimethylamino)methyl)phenyl]palladium], together with both bis(2-(arylazo)aryl)palladium and bis(2-((dimethylamino)methyl)phenyl)palladium. The X-ray structures of cis-[(bis(2-phenylazo)phenyl)palladium] and of cis-[(2-((dimethylamino)methyl)phenyl)-(2-(phenylazo)phenyl)palladium] have been determined and compared with those of known related molecules. The ((arylazo)aryl)palladium complexes fail to insert alkenes. Bis(2-((dimethylamino)methyl)phenyl]-palladium is shown to insert both styrene and carbon monoxide, and the efficient insertion of methyl acrylate into bis[(2-((tert-butylimino)methyl)phenyl)chloropalladium] is also described. ß-Elimination following insertion leads to the palladium-free product in each case. © 1987 American Chemical Society.