Oxidative addition reaction of o-quinones to triphenylantimony: novel triphenylantimony catecholate complexes

Cherkasov, V. K.; Grunova, Ekaterina; Poddel’sky, Andrey I.; Fukin, Georgy K.; Kurskii, Yury A.; Abakumova, L. G.; Абакумов, Г. А.

doi:10.1016/j.jorganchem.2004.11.049

Cited by 55 publications

(26 citation statements)

References 10 publications

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“…24 [6 tert Butyl 4 (5 tert butyl 2 methyl 3,4 dioxo cyclohexa 1,5 dien 1 yl) 3 methylcatecholato]triphenyl antimony(v) was prepared by a previously described method. 12 The ESR spectra were recorded on a Bruker ER 200 D SRC spectrometer equipped with a ER 4105 DR double cavity and ER 4111 VT thermal controller. The spectra were simulated using the WinEPR SimFonia v1.25 program (Bruker).…”

Section: Methodsmentioning

confidence: 99%

ESR investigation of paramagnetic derivatives of [6-tert-butyl-4-(5-tert-butyl-2-methyl-3,4-dioxocyclohexa-1,5-dien-1-yl)-3-methylcatecholato]triphenylantimony(V)

2005

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A number of paramagnetic derivatives of [6 tert butyl 4 (5 tert butyl 2 methyl 3,4 dioxocyclohexa 1,5 dien 1 yl) 3 methylcatecholato]triphenylantimony(V) were investigated by ESR spectroscopy. The reactions of this complex with Cр 2 Cо or LiCl in the presence of Hg metal. lead to the formation of free (nonchelated) radical anion semiquiones. Chelated complexes are formed in the case of Tl(Hg), Mn 2 (CO) 10 , Re 2 (CO) 10 , Sn 2 Ph 6 , Cu(met.), and CuCl + dppfc (dppfc is bis diphenylphosphinoferrocene). Key words: ESR spectroscopy, di o quinone, o semiquinonato metal complexes, catecholatotriphenylantimony(v).An important and promising line of research in the chemistry of о semiquinone metal complexes is the study of intramolecular electronic interactions (metal-ligand, metal-metal, ligand-ligand), depending on the molecu lar geometry and the system behavior. The topicality of the studies in this field is related to the search for new approaches to the design of molecular electronic de vices 1-3 and molecular magnets, 4-6 being developed in tensively in recent years. Of particular interest in this respect are di о quinones, able to form bi and poly nuclear complexes with bridging paramagnetic ligands. Their use provides new opportunities for the synthesis of high spin systems and bi stable metal complexes. Two types of derivatives of this sort are now known. A series of homometal binuclear di o semiquinone complexes (1a,b) have been reported. 7,8 In these complexes, the ligand ex ists as so called "nonalternate biradical" whose structure ensures the ferromagnetic type of the exchange between the radical centers.Previously, 9-11 we reported the synthesis and the structures of a number of mono , bi , and polynuclear complexes derived from 4,4´ di (6 tert butyl 3 methyl benzo 1,2 quinone) (2). The reduction of 2 may yield three paramagnetic species: radical monoanion, radical dianion, and radical trianion. A number of examples have been reported for the first two species, quinone semi quinone and di semiquinone derivatives. 9,10 For the third type, i.e., the catecholato semiquinone form, only one example is known: the tripotassium salt. 11Heteronuclear complexes derived from 2 have not been described until recently. Recently, we obtained, by oxi dative addition, quinone catecholate (3), 12 which served as the starting synthon for the synthesis of catecholato semiquinone derivatives.This communication presents a ESR study of para magnetic heteronuclear complexes obtained by the re duction of quinone catecholate (3).

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Section: Methodsmentioning

confidence: 99%

ESR investigation of paramagnetic derivatives of [6-tert-butyl-4-(5-tert-butyl-2-methyl-3,4-dioxocyclohexa-1,5-dien-1-yl)-3-methylcatecholato]triphenylantimony(V)

2005

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“…However, recently, we found that antimony o -amidophenolate complexes are able to add and eliminate dioxygen [4] under mild conditions. As opposed to this, antimony catecholate complexes, 3,6-di-tert -butylcatechol derivatives, which do not differ much from amidophenolates, do not react with dioxygen under similar conditions [5]. The reaction mechanism proposed previously [4] assumes that one-electron oxidation of the dianionic ligand to a radical anion is a key step of the process.…”

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confidence: 94%

Cyclic Endoperoxides Based on Triphenylantimony(V) Catecholates: The Reversible Binding of Dioxygen

et al. 2005

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“…4 For ex ample, the reaction of pyrocatechol produces antimony(V) triphenylcatecholate. The reaction of resorcinol gives 3,3,3,11,11,11 hexaphenyl 2,4,10,12 tetraoxa 3,11 di stibatricyclo[11.3.1.1 5,9 ]octadeca 1,5,6,8,13,15 hexaene, in which each antimony atom is bound to the oxygen atoms of two different resorcinol fragments. The reaction of hydroquinone affords polymeric triphenylantimony(V) hydroquinolate.…”

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confidence: 99%

“…For example, 1 is quantita tively oxidized with o quinones to the corresponding antimony(V) catecholates. 5 The reaction of 1 with 2 (Scheme 1) under consider ation is of interest because molecule 2 contains two fragments, quinone and hydroperoxide, with poten tial oxidative activity. The arrangement of the oxygen atoms in compound 2 allows the formation of cate cholate, dimeric, or polymeric derivatives of anti mony(V).…”

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confidence: 99%

“…In both solvents, the signals of the starting reagents disappeared within 2-3 min after mixing of compounds 1 and 2 in a ratio of 1 : 1. Taking into account the structure of the known reaction product of 1 with resorcinol 4 and the NMR spectra of the reaction mixture, the reaction most probably pro duces 1,7,9,15,17,18 hexaisopropyl 3,3,3,11,11,11 hexaphenyl 2,4,10,12 tetraoxa 3,11 distibatri cyclo[11.3.1.1 5,9 ]octadeca 5,7,13,15 tetraene 6,14 dione (4) (see Scheme 1).…”

mentioning

confidence: 99%

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Oxidation of triphenylantimony with 4-hydroperoxy-2-hydroxy-3,4,6-triisopropylcyclohexa-2,5-dienone or 3,4,6-triisopropyl-1,2-benzoquinone

et al. 2007

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According to the NMR spectroscopic data, the oxidation of triphenylantimony with 4 hydroperoxy 2 hydroxy 3,4,6 triisopropylcyclohexa 2,5 dienone involves three steps. The first step affords the 2,4,10,12 tetraoxa 3,11 distibatricyclo[11.3.1.1 5,9 ]octadecatetraene de rivative. The latter is rearranged into benzodioxastibolone derivatives followed by the rear rangement into 4,6,7 triisopropyl 2,2,2 triphenyl 1,3,2 benzodioxastibol 5 ol. The transfor mation of the latter depends on the presence of oxygen and the mode of its dosing.

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Oxidative addition reaction of o-quinones to triphenylantimony: novel triphenylantimony catecholate complexes

Cited by 55 publications

References 10 publications

ESR investigation of paramagnetic derivatives of [6-tert-butyl-4-(5-tert-butyl-2-methyl-3,4-dioxocyclohexa-1,5-dien-1-yl)-3-methylcatecholato]triphenylantimony(V)

ESR investigation of paramagnetic derivatives of [6-tert-butyl-4-(5-tert-butyl-2-methyl-3,4-dioxocyclohexa-1,5-dien-1-yl)-3-methylcatecholato]triphenylantimony(V)

Cyclic Endoperoxides Based on Triphenylantimony(V) Catecholates: The Reversible Binding of Dioxygen

Oxidation of triphenylantimony with 4-hydroperoxy-2-hydroxy-3,4,6-triisopropylcyclohexa-2,5-dienone or 3,4,6-triisopropyl-1,2-benzoquinone

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