Manganese(III) and rhenium(II) complexes with bulky 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinonato ligands via carbonyls of corresponding metals

Абакумов, Г. А.; Poddel’sky, Andrey I.; Bubnov, M. P.; Fukin, Georgy K.; Abakumova, L. G.; Ikorskiǐ, V. N.; Cherkasov, V. K.

doi:10.1016/j.ica.2005.07.003

Cited by 29 publications

(41 citation statements)

References 32 publications

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“…The more diffuse orbitals and lower electronegativity of the nitrogen donor atoms in o-iminobenzosemiquinone and odiiminobenzosemiquinone radical ligands have been found to provide better orbital overlap within the metal-nitrogen bond, leading to an increase in the strength of the exchange coupling [122][123][124][125][126][127][128][129][130][131]. Moreover, functionalization at the nitrogen atoms allows control of the steric hindrance at the metal center and ultimately the electronic environment of the ligand.…”

Section: Benzosemiquinonoid Radical-containing Complexesmentioning

confidence: 99%

Radical ligand-containing single-molecule magnets

Demir

Jeon

Long

et al. 2015

Coordination Chemistry Reviews

542

386

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Section: Benzosemiquinonoid Radical-containing Complexesmentioning

confidence: 99%

Radical ligand-containing single-molecule magnets

Demir

Jeon

Long

et al. 2015

Coordination Chemistry Reviews

542

386

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“…[ (35)) were synthesized from four-coordinate Mn(ISQ L2 )(AP L2 ) (69, see Section 6.8) by dilution of this compound in corresponding solvent [61] or from manganese(II) salt and o-iminobenzosemiquinonato thallium salt (molar ratio is 1:2) in a suitable solvent medium [59].…”

Section: Synthesismentioning

confidence: 99%

“…We have found only seven examples of such complexes in the literature. There is a nickel complex [Ni II (IBQ L4 ) 2 (OClO 3 ) 2 ] (36) [62], rhenium complex Re II (ISQ L2 ) 2 (CO) 2 (37) [61] and a number of zirconium complexes Zr IV (AP tBu ) 2 (THF) 2 (38), [63,64] (Scheme 12).…”

Section: Hexacoordinate Bis-o-iminobenzoquinonato Complexes Of M(isq)mentioning

confidence: 99%

“…The nickel complex 36 is a product of the oxidation of bis-oiminobenzosemiquinonato nickel(II) complex Ni(ISQ L4 ) 2 (45, see Section 6.2) with two equivalents of AgClO 4 ·H 2 O [62] while the rhenium complex Re II (ISQ L2 ) 2 (CO) 2 (37) was prepared from rhenium carbonyl and o-iminobenzoquinone IBQ L2 under UV in toluene [61]. This synthetic method will also be considered in Section 6.1.…”

Section: Synthesismentioning

confidence: 99%

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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

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324

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“…[5][6][7] The introduction of alkyl substituents at positions 2 and 6 leads to stabilization of low coordinated cobalt and manganese compounds, in which these metals have an unusual coordination number of 4. 8, 9 Since the metal atoms in these complexes are coordinatively unsaturated, small molecules and atoms can additionally be bonded to form five coordinate complexes. 8- 10 The preparation of mixed ligand complexes of composition ML 2 X, where X is halogen, offers possibilities for the synthesis of com plexes containing radical ligands of different nature.…”

mentioning

confidence: 99%

Synthesis and structures of five-coordinate bis-o-iminobenzosemiquinone complexes M(ISQ-R)2X (X = Cl, Br, I, or SCN; M = CoIII, FeIII, or MnIII)

et al. 2006

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New five coordinate complexes Co(ISQ Pr i ) 2 Cl, Co(ISQ Me) 2 Cl, Co(ISQ Me) 2 I, Co(ISQ Me) 2 (SCN), Mn(ISQ Pr i ) 2 Cl, and Fe(ISQ Me) 2 Br (ISQ Pr i and ISQ Me are the 4,6 di tert butyl N (2,6 diisopropylphenyl) and 4,6 di tert butyl N (2,6 dimethylphenyl) o iminobenzosemiquinone radical anions, respectively) were synthesized. The complexes were characterized by UV Vis and IR spectroscopy and magnetochemistry. The molecular struc tures of the Fe(ISQ Me) 2 Br and Mn(ISQ Pr i ) 2 Cl complexes were established by X ray diffrac tion. The singlet ground state (S = 0) of the cobalt complexes is caused by antiferromagnetic coupling between the unpaired electrons of the radical ligands (S = 1/2) through the fully occupied atomic orbitals of low spin cobalt(III) (d 6 , S = 0). The effective magnetic moments of the complexes at 10 К are 0.18 µ B for Co(ISQ Pr i ) 2 Cl and 0.16 µ B for Co(ISQ Me) 2 I. The ground state of the manganese complex is triplet (S = 1). Two unpaired electrons of the o iminobenzosemiquinone ligands are strongly antiferromagnetically coupled with two of four unpaired electrons of high spin manganese(III) (d 4 , S = 2).Abundant data on o semiquinone complexes have been accumulated. 1,2 Studies of metal complexes with o imino benzoquinone ligands (analogs of o benzoquinones) are of considerable interest because o iminobenzoquinones have distinguishing features due to which such studies extend the range of related compounds and add to our knowledge of this class of complexes.Unlike o quinones, o iminoquinones are asymmetric, and the presence of the nitrogen atom allows one to in vestigate the spin density distribution in the chelate ring. The use of o iminosemiquinone as a spin labeled ligand in metal complexes helps in solving structural dynamic problems 3 and makes it possible to determine the spatial arrangement of ligands containing magnetic nuclei with respect to the plane of the o iminosemiquinone plane. 4 At the same time, o iminosemiquinones, like o semi quinones, serve as magnetic centers. From this stand point, investigation of spin couplings between ligands and/or between ligands and metals are of interest.The steric hindrance of the metal centers in com plexes can be varied over a wide range by introducing various substituents at the nitrogen atom. For example, o iminobenzoquinones containing the unsubstituted phe nyl substituent at the nitrogen atom form tris ligand tran sition metal complexes, which are very similar to o semi quinone derivatives. 5-7

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Manganese(III) and rhenium(II) complexes with bulky 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinonato ligands via carbonyls of corresponding metals

Cited by 29 publications

References 32 publications

Radical ligand-containing single-molecule magnets

Radical ligand-containing single-molecule magnets

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

Synthesis and structures of five-coordinate bis-o-iminobenzosemiquinone complexes M(ISQ-R)2X (X = Cl, Br, I, or SCN; M = CoIII, FeIII, or MnIII)

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