Comparative studies on charge distribution for the ruthenium and osmium quinone complexes [M(bpy)2(quinone)]n (M = Ru, Os; n = 0, +1, +2)

Haga, Masaaki; Isobe, Kiyoshi; Boone, Steven R.; Pierpont, Cortlandt G.

doi:10.1021/ic00344a029

Cited by 64 publications

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“…Therefore, short bond lengths of 1.36 ± 1.37 are observed for the C(19) ± C (20) and C(21) ± C (22) bonds. On the other hand, the C(17) ± C (18) and C(20) ± C(21) bonds are considerably lengthened (1.44 ± 1.45 ). Considering that the dioxolene moiety can be unambiguously identified as a semiquinonate, the short Fe ± N bonds must therefore result from the low-spin state of the iron(iii) ion.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, a quite intense absorption band at a rather similar position has been observed for [Ru(bipy) 2 (dbq)] 2 (l 668 nm, e 14 100 m À1 cm À1 ) [17] and [Os(bipy) 2 (dbsq)] 2 (l 558 nm). [18] Since a low-spin osmium(iii) ion is thought to be coordinated to a semiquinonate in the osmium complex, the absorption band was assigned to a LMCT transition. In contrast, based on the fact that the ruthenium complex is regarded as containing a low-spin ruthenium(ii) ion coordinated to a benzoquinone, the band at 668 nm was assigned to a MLCT transition.…”

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confidence: 99%

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Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

Koch¹,

Schünemann²,

Gerdan³

et al. 1998

Chem. Eur. J.

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The reaction of iron(ii) perchlorate with the tetraazamacrocyclic ligand N,N'-dimethyl-2,11-diaza[3.3]-(2,6)pyridinophane (L-N 4 Me 2 ) and 3,5-di-tert-butyl-1,2-benzoquinone in 96 % ethanol yields the blue compound Me 2 )(dbsq)](ClO 4 ) 2´2 .5 H 2 O (3 a, dbsq À 3,5-di-tert-butyl-1,2-benzosemiquinonate). On the basis of structural, Mössbauer spectroscopic, and magnetic evidence, this compound was identified as a low-spin iron(iii) semiquinonate complex, the first of its kind, in which the unpaired electron of the coordinated semiquinonate radical is strongly antiferromagnetically coupled with the unpaired electron of the lowspin iron(iii) ion. In acetonitrile solution, Me 2 )(dbsq)] 2 (3) is in equilibrium with uncoordinated dbq and with the low-spin iron(ii) complex ions. Solutions of complex 3 in acetonitrile are found to be stable towards molecular oxygen. In addition, the reaction of the iron(iii) semiquinonate complex 3 with superoxide quantitatively yields the corresponding iron(iii) catecholate complex Me 2 )(dbc)](2). Therefore, the reactivity of 3 with molecular oxygen and with superoxide demonstrates that the correct oxidation states of both the metal ion and the coordinated dioxolene unit are required for the occurrence of the well-established cleavage of the intradiol C ± C bond of 3,5-di-tert-butylcatecholate ligand coordinated to the iron(iii) ion in 2 by molecular oxygen and that the cleavage reaction does not occur through an initial electron-transfer step, resulting in the formation of an iron(iii) semiquinonate as intermediate, but instead by the direct attack of the oxygen molecule on the iron(iii) catecholate moiety.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

Koch¹,

Schünemann²,

Gerdan³

et al. 1998

Chem. Eur. J.

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“…Compared to the usually observed range of d 0.4 ± 0.6 mm s À1 for other six-coordinate high-spin iron(iii) complexes containing this tetraazamacrocyclic ligand, the present value for d is significantly reduced. Also taking into account (18) 1.329 (5) 1.368 (8) 1.296(5) C(17) ± C (18) 1.415 (7) 1.411 (10) 1.450(7) C(17) ± C (22) 1.385 (7) 1.380 (10) 1.403(7) C(18) ± C (19) 1.394 (6) 1.409 (10) 1.425(7) C(19) ± C (20) 1.369 (8) 1.396 (10) 1.370(7) C(20) ± C(21)…”

Section: Resultsmentioning

confidence: 99%

Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

et al. 1998

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“…This illustrates a large contribution of a metal-centered state [Os III (AP L1 )(bipy)](PF 6 ). The heavier osmium stabilizes the higher oxidation state relative to the ruthenium homologue [13,51]. For comparison, the o-iminobenzosemiquinonato osmium(III) complexes Os III (PPh 3 )(ap-R)(ISQ Me ), where ap-R is tridentate dianionic ligands derived from 2-arylazo-4-methylphenol (aryl is p-methoxyphenyl, p-tolyl, phenyl, p-chlorophenyl and p-nitrophenyl), ISQ Me is radical-anion 4-methyl-o-iminobenzosemiquinone, were reported to be diamagnetic due to antiferromagnetic coupling of the low-spin osmium(III) (d 5 , S = 1/2) with the o-iminobenzosemiquinonato unpaired electron [52].…”

Section: Structure and Magnetismmentioning

confidence: 99%

Transition metal complexes with bulky 4,6-di-tert-butyl-N-aryl(alkyl)-o-iminobenzoquinonato ligands: Structure, EPR and magnetism

Poddel’sky

Cherkasov

Abakumov

2009

Coordination Chemistry Reviews

319

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Comparative studies on charge distribution for the ruthenium and osmium quinone complexes [M(bpy)2(quinone)]n (M = Ru, Os; n = 0, +1, +2)

Cited by 64 publications

References 0 publications

Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

Structural, Spectroscopic, and Chemical Properties of the First Low-Spin Iron(III) Semiquinonate Complexes in the Solid State and in Solution

Transition metal complexes with bulky 4,6-di-tert-butyl-N-aryl(alkyl)-o-iminobenzoquinonato ligands: Structure, EPR and magnetism

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