Palladium-Assisted Formation of Carbon−Carbon Bonds. 7.¹ Reactions of (2,3,4-Trimethoxy-6-X-phenyl)palladium Complexes with Alkynes (X = C(O)NHBut) and Isocyanides (X = C(O)NHBut, C(O)Me, CHO):  Crystal and Molecular Structures of [Pd{C₆H{C(O)NHBut}-6-(OMe)₃-2,3,4}(bpy)](CF₃SO₃), [Pd{C(CO₂Me)C(CO₂Me)C₆H{C(O)NHBut}-6-(OMe)₃-2,3,4)}- Cl(PPh₃)], [Pd{C(NXy)C₆H{C(O)NHBut}-6-(OMe)₃-2,3,4}- (bpy)](CF₃SO₃), and the Ketenimine 2-(2,6-Dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)- methylene)-5,6,7-trimethoxy-3-oxoisoindoline

The mercuriation of 3,4,5-trimethoxy( N - tert -butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction with KCl leads to the formation of [Hg{C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}Cl] ( 1 ), which is symmetrized with [NMe 4 ]Cl to give [Hg{C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4} 2 ] ( 2 ). The reaction of 2 with [PdCl 2 (MeCN) 2 ] and 2,2‘-bipyridine (bpy) affords [Pd(C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4)Cl(bpy)] ( 3 ), which reacts with Tl(CF 3 SO 3 ) Complex 2 reacts with [PdCl 2 (MeCN) 2 ] and acetylenes RC⋮CR to give metallic palladium and the spirocyclic compound 10-( N - tert- butylcarbamoyl)-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]-1,3,6,9-decatetraen-8-one ( 5 ) when R = Ph or the monoinserted palladium ( 6 ) when R = CO 2 Me. By reaction of 6 with L (1:2) or PPh 3 and Tl(CF 3 SO 3 ) (1:4:2), the = PPh 3 ( 7 ), CNXy ( 8 ) (Xy = 2,6-dimethylphenyl)) are obtained respectively. The reactions of 4 and of the related or [Pd{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(NCMe)(bpy)](CF 3 SO 3 ) ( 11 ) with CNXy have also been studied, the following compounds being ( 12 ) [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) ( 13 ), [Pd{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) ( 14 ), and the ketenimine 2-(2,6-dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)methylene)-5,6,7-trimethoxy-3-oxoisoindoline ( 15 ). The structures of 4, 7, 12, and 15 have been determined by X-ray crystallography.