Reactivity of ortho ‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Complexes [Pd(C 6 H 3 XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO 2 ; N^N= N , N , N′ , N′ ‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐ tert ‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RNCE (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′ 2 ) and TlOTf (OTf=CF 3 SO 3 ) to give, respectively, 1) products of the insertion of the CE group into the CPd bond, protonation of the N atom, and coordination of X to Pd, [Pd{ κ 2 ‐ X , E ‐(XC 6 H 3 {EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd( κ 2 ‐ X , N ‐{ZC 6 H 3 (NHCR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{ κ 2 ‐ C , N ‐(C 6 H 4 {OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd( κ 2 ‐ X , N ‐{XC 6 H 3 (NHCR)‐2‐R′‐4})(N^N)]OTf.