Formation, structure, and reactivities of 1:1 adducts between quadricyclane and (η5-cyclopentadienyl)(1,2-diphenyl- or -dimethoxycarbonyl-1,2-ethenedithiolato)rhodium(III)

Diverse reactivities of aromaticity–unsaturation coexisted metalladithiolene rings

“…One product, which was structurally determined, was a norbornene-bridged adduct (35, 40% yield) [77]. In the case of [CpRh(dphedt)] (34) or [CpRh(dcmedt)] (27) complex, we found a single isomer of the norbornene adduct (Scheme 2(b), 85% (36) or 81% (37) yield) but these structures of Rh adducts were different from the cobalt complex [78]. In the cobalt complex 35, the edge carbon of norbornene moiety is bound to the Co atom and the bridge carbon is attached to the S atom ( Fig.…”

“…On the other hand, even if the deuteriumlabeled Rh adduct 36-d, which was formed in the reaction of complex 34 and deuterium-labeled Q-d, is refluxed in unlabeled Q, the hydrocarbon unit of the adduct 36-d did not exchange from that with unlabeled Q [78]. When adducts 36 and 37 were used as catalysts, they also showed the catalytic activity (TN).…”

“…Upon irradiation in a dichloromethane solution with a medium pressure mercury lamp, the adduct 36 is dissociated to form the corresponding original complex 34 and NBD, accompanied by a skeletal rearrangement in the hydrocarbon moiety (C 7 H 8 ). A study using Dlabeled adduct revealed that NBD was formed in a mechanism involving reverse skeletal rearrangement (Scheme 7) [78]. …”

“…The oneelectron oxidation of the norbornene-bridged adduct 36 gave the free complex 34. Therefore, formal generation of norbornadiene cation was considered [78]. We also studied the electrochemical behavior of X coordinated or PR 3 coordinated S-alkyl complexes as shown in Scheme 4, and also the analog imido complexes as shown in Scheme 5.…”

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

“…Addition reactions are observed on the CoeS bond in the cobaltadithiolene ring [6]. The formed cobaltadithiolene adducts can be dissociated by thermal [7], photochemical [8] and other chemical reactions [9] toward rearomatized cobaltadithiolene complexes.…”