Two near-UV and visible chromophores of CpCo(Dithiolene) complexes with pyridinium-dicyanomethylide group

Nomura, Mitsushiro; Kanamori, Mami; Tateno, Naoki; Fujita-Takayama, Chikako; Sugiyama, Toru; Kajitani, Masatsugu

doi:10.1016/j.jorganchem.2010.07.011

Cited by 3 publications

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“…The reaction of [CpCo(S 2 C 2 ( 4 Py) 2 )] (43) with 2 equiv of TC-NEO in refluxing THF produced [CpCo(S 2 C 2 ( 4 Py)( 4 Py-C(CN) 2 ))] (44) with one dicyanomethylide group and [CpCo(S 2 C 2 ( 4 Py-C(CN) 2 ) 2 )] (45) with two dicyanomethylide groups in 21% and 59% yields, respectively (Scheme 11). 80 The reaction of [CpCo(S 2 C 2 ( 2 Py) 2 )] (49) with TCNEO was performed but unfortunately no dicyanomethylation occurred. The only product, which could be identified, was the corresponding di-2pyridylacetylene (50, 2 Py-C C-2 Py) in ca.…”

Section: Reactions Of Pyridyl-substituted Dithiolene Complexes With E...mentioning

confidence: 99%

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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: Reactions Of Pyridyl-substituted Dithiolene Complexes With E...mentioning

confidence: 99%

“…30% yield (Scheme 11). In addition, [CpCo(S 2 C 2 ( 2 Py)( 4 Py))] ( 46 80 This suggests that a dicyanomethylation is also possible to the 3-pyridyl group.…”

Section: Reactions Of Pyridyl-substituted Dithiolene Complexes With E...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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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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Synthesis and Electrochemistry of Organometallic Cobaltadithiaazulenes

et al. 2012

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Reaction of tropolone or hinokitiol with phosphorus pentasulfide (P(2)S(5)) directly gives the sulfurized precursor [PS(2)(SST)](2) or [PS(2)(SSH)](2) (SST = dithiotropolonato or SSH = dithiohinokitiolato). The resulting [PS(2)(SST)](2) or [PS(2)(SSH)](2) is further reacted with [CpCoI(2)(CO)] (Cp = η(5)-cyclopentadienyl) to form the organometallic [CpCo(I)(SST)] (1) or [CpCo(I)(SSH)] (2), respectively. 1 and 2 have a cobaltadithiaazulene ring containing one cobalt and two sulfur atoms in the five-membered ring of azulene. Although X-ray structure analysis of 1 reveals the iodide-coordinated structure, 1 becomes the iodide-free complex [CpCo(SST)](+) (4(+)) in solution. Electrochemical studies of 4(+) by CV and spectroelectrochemical measurements (ESR, UV-vis-NIR) in solution are carried out. 4(+) is stepwise reduced by 2e(-) to form the stable neutral radical (4(•)) and unstable anion (4(-)). It is proposed that the anion 4(-) undergoes dimerization to afford the dimer (6(2-)) by anion radical coupling at the 5 or 7 position in the seven-membered ring of the cobaltadithiaazulene, since the similar anion radical coupling of a reduced azulene has been reported. Electrochemical reoxidation of 6(2-) slowly undergoes monomerization, giving the original monomer 4(•). DFT calculation of 4(+) explains that there is a delocalized lowest unoccupied molecular orbital (LUMO) in the whole molecule, and that of radical 4(•) has a delocalized singly occupied molecular orbital (SOMO). In these CpCo-SST (or SSH) complexes, there could be metal/ligand electron transfer since the SST (or SSH) ligand is potentially redox active. The spin density distribution of 4(-) obtained by the DFT method supports the mechanism of the anion radical coupling at the 5 or 7 position in the seven-membered ring.

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Two near-UV and visible chromophores of CpCo(Dithiolene) complexes with pyridinium-dicyanomethylide group

Cited by 3 publications

References 79 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

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

Synthesis and Electrochemistry of Organometallic Cobaltadithiaazulenes

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