Rare direct imidation of aromatic metallacycle by reaction of CpCo(dithiolene) complex with N-halosuccinimide

Organometallic dithiolene complexes of the group 8–10 metals: Reactivities, structures and electrochemical behavior

“…[CpCo(S 2 C 2 (R 1 )(H))] (R 1 = Ph, Me, 9-phenanthryl, H) complexes were reacted with N-halosuccinimides (NXS; X = Cl, Br, I) in carbon tetrachloride at room temperature to give the Nsuccinimide substitution product (33, Scheme 9(d)), 72 but unexpectedly no halogenated dithiolene complex was obtained. The reaction of NIS gave a relatively higher yield of 33 (28-64%) compared with those of NCS (4-15%) and NBS (5-9%).…”

“…The reaction of [CpCo(S 2 C 2 H 2 )] (R 1 = H) with NIS afforded the double imidation product (35, 9% yield). 72 Note that the substitution of succinimide group to the cobaltadithiolene ring by NXS is the rare case of direct imidation to an aromatic metallacycle. The formation of homo-coupling products 34 can be explained by a Lewis acid effect of the succinimide moiety.…”

Pd-catalyzed boronations and cross-coupling reactions of aromatic cobaltadithiolene complexes with aryl halides

“…CCDC 808149 (11), 808150 (12), 808151 (13), 808152 (14), 808153 (7), 808154 (9); contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.…”

“…Recently, we focused on some coupling reactions of the cobaltadithiolene ring, because it is one representative reactivity of an aryl group. The treatments of [CpCo(S 2 C 2 (R)(H))] (R ¼ Me, Ph, 9-phenanthryl) with a protic acid or Lewis acid give dithioleneedithiolene homo-coupling products (Chart 1) [13]. Nishihara et al reported the homo-coupling reaction of [CpCo(S 2 C 2 H 2 )] with HX acid to afford the trinuclear complex [CpCo(S 2 C 2 )] 3 (Chart 1) [14].…”

“…Nishihara et al reported the homo-coupling reaction of [CpCo(S 2 C 2 H 2 )] with HX acid to afford the trinuclear complex [CpCo(S 2 C 2 )] 3 (Chart 1) [14]. In addition, we have reported the formations of similar homo-coupling products by the reactions of [CpCo(S 2 C 2 (R)(H))] with N-halosuccinimides (NXS) although the unexpected imidation products [CpCo(S 2 C 2 (R)(N-succinimide))] are mainly formed [13].…”