Sulfur-centered and nitrogen-centered radical substitution reactions of aromatic CpCo(dithiolene) complex with 2,2′-Dibenzothiazolyl disulfide

Nomura, Mitsushiro; Oguro, Hiroki; Maeshima, Kazuaki; Iida, Suguru; Horikoshi, Satoshi; Sugiyama, Toru; Sugimori, Akira; Kajitani, Masatsugu

doi:10.1016/j.jorganchem.2010.03.032

Cited by 8 publications

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References 31 publications

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“…2-Benzothiazolylthiyl radical (RS ∑ ) was substituted on the Me group or on the dithiolene ring of [CpCo(medt)] to give [CpCo(S 2 C 2 (CH 2 SR)(H))] (29, 4-23% yields) or [CpCo(S 2 C 2 (Me)(SR))] (30, 6-24% yields), respectively (Scheme 9(b)). 71 Thermal reactions, photochemical reactions and MWenhanced reactions were effective. The reaction of [CpCo(phedt)] with RSSR gave two different substitution products on the dithiolene ring but they were structural isomers.…”

Section: Substitution Reactions and Coupling Reactions On The Dithiol...mentioning

confidence: 99%

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

Nomura

2011

Dalton Trans.

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Research progress in the organometallic dithiolene complexes such as [Cp(or Cp*)M(dithiolene)] (M = Co, Rh, Ir, Ni), [(C(6)R(6))Ru(dithiolene)] and [(C(4)R(4))Pt(dithiolene)] complexes during the past decade is described and the reactivities, structures and electrochemical behavior are summarized in this paper. The five-membered metalladithiolene ring (MS(2)C(2)) undergoes addition reactions to the M[double bond, length as m-dash]S bond to form 18-electron adducts by an imido, alkylidene, alkene or norbornene group and also undergoes dimerizations on the basis of the unsaturation in the ring. The aromaticity of the ring causes substitution reactions on the dithiolene carbon by a C-centered radical, S-centered radical or succinimide group when the ring has a C-H bond. Furthermore a dithiolene-dithiolene homo-coupling reaction by an acid or dithiolene-aryl cross-coupling occurs based on the aromaticity in the ring. Dissociations of the 18-electron adducts are observed by those thermolyses, photolyses, electrochemical redox reactions and other chemical reactions with tertiary phosphorus compounds. One representative example of them is the imido adduct dissociation with PR(3) under heating toward the intramolecular imido migration to a Cp ligand. Since all products are rearomatized by those adduct dissociations, it is concluded that the 'coexistence of aromaticity and unsaturation' in the metallacycle mediates the diverse chemical reactions.

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Section: Substitution Reactions and Coupling Reactions On The Dithiol...mentioning

confidence: 99%

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

Nomura

2011

Dalton Trans.

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“…On the basis of the aromaticity, we have observed electrophilic substitution reactions on the dithiolene carbon with acyl chloride toward 68 (Scheme 13(a)) [112], radical substitution reactions with carbon-centered radical generated from 2,2 0 -azobis(isobutyronitrile) to form 69 (Scheme 13 (b)) [112,113], and with sulfur-centered radical (Scheme 13(c)) or with nitrogen-centered radical generated from 2,2 0 -dibenzothiazolyl disulfide (Scheme 13(d)) toward 71e74 [114]. Formation mechanisms for 71e74 are probably similar to those of typical organic radical reactions; thus, addition of sulfur radical to the dithiolene carbon radical or to the CH 2 group followed by the radical hydrogen abstraction from the dithiolene ring or Me group.…”

Section: Substitution Reactions Of Aromatic Cpco(dithiolene) Complexesmentioning

confidence: 99%

Diverse reactivities of aromaticity–unsaturation coexisted metalladithiolene rings

Nomura

Fujita-Takayama

Sugiyama

et al. 2011

Journal of Organometallic Chemistry

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“…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.…”

Section: Acknowledgmentmentioning

confidence: 99%

“…The ring undergoes electrophilic substitution reactions (Friedel-Crafts type) [10], carbon-centered [10,11], sulfur-centered and nitrogen-centered radical substitution reactions [12]. Recently, we focused on some coupling reactions of the cobaltadithiolene ring, because it is one representative reactivity of an aryl group.…”

Section: Introductionmentioning

confidence: 99%

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

Nomura

Terada

Onozawa

et al. 2011

Journal of Organometallic Chemistry

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Sulfur-centered and nitrogen-centered radical substitution reactions of aromatic CpCo(dithiolene) complex with 2,2′-Dibenzothiazolyl disulfide

Cited by 8 publications

References 31 publications

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

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

Diverse reactivities of aromaticity–unsaturation coexisted metalladithiolene rings

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

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