Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

Cuevas, Alicia; Geis, L.; Pintos, V.; Chiozzone, Raúl; Sanchiz, Joaquı́n; Hummert, Markus; Schumann, Herbert; Kremer, Carlos

doi:10.1016/j.molstruc.2008.12.031

Cited by 10 publications

(12 citation statements)

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“…K 2 ReCl 6 was prepared following a literature procedure [13]. This compound was transformed into the tetrabutylammonium salt, (NBu 4 ) 2 (NBu 4 )[ReCl 4 (cat)]ÁH 2 cat was prepared as previously described [10]. 2-Propanol was stored under Linde type 4 Å molecular sieves to reduce the water content.…”

Section: Methodsmentioning

confidence: 99%

“…The synthesis, characterization and spectroscopic characterization of the novel Re(IV) complex (HNEt 3 )(NBu 4 )[ReCl 4 (H 2 L)] is also included. The results are compared with the one previously reported [10] for (HNEt 3 )(NBu 4 )[ReCl 4 (cat)].…”

Section: Introductionmentioning

confidence: 92%

“…The most intense peaks appear at 1617, 1580 (ACH@NA stretching), 1460 and 1282 cm À1 . Previous reported works [10,[30][31][32] have assigned the last three peaks to different stretching modes, AHC@N, CAC, and CAO. Tert-butyl stretching frequencies at 2961, 2934, and 2873 cm À1 , and ReACl stretching bands at 377, 329, and 302 cm À1 are also noticeable.…”

Section: Synthesis Characterization and Spectroscopic Properties Ofmentioning

confidence: 98%

“…The first Re(IV) complex with a catecholate ligand was very recently reported by us [10]. The crystal structure of (HNEt 3 ) (NBu 4 )[ReCl 4 (cat)]ÁH 2 cat (H 2 cat = catechol) contains the rhenium ion in a distorted octahedral geometry, being bonded to a bidentate catecholate group and four chloride anions.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Structural and theoretical studies of (E,E)-benzaldehyde azine and its rhenium(IV) complex

Pintos

Cuevas

Onetto

et al. 2010

Journal of Molecular Structure

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

Section: Synthesis Characterization and Spectroscopic Properties Ofmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structural and theoretical studies of (E,E)-benzaldehyde azine and its rhenium(IV) complex

Pintos

Cuevas

Onetto

et al. 2010

Journal of Molecular Structure

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“…Rhenium(IV) compounds have recently been investigated by many research groups because of their interesting magnetic properties [1][2][3][4]. One of the first syntheses of complexes of [ReX 5 Py] -type was described in 1963, when Babeshkina and Tronev [5] reported the compounds pyH[ReX 5 (py)], (X = Cl, Br), and in 1971, Tisley and Walton [6] obtained (NEt 4 ) 2 [ReCl 5 (py)], but the crystal structures were not determined.…”

Section: Introductionmentioning

confidence: 99%

Solvothermal synthesis, characterization and properties of [ReCl5(py)]− complex with T (Néel) of 5.5 K

Kochel

2009

Transition Met Chem

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The synthesis and properties of a rhenium(IV) complex with pyridine as a ligand are presented. The complex, with the formula (2-methyl-pyH)[ReCl 5 (py)] 4,4 0 -bipyridyl 1 has been characterized by elemental analysis, IR spectroscopy, SQUID and X-ray measurements. The single crystal X-ray structure of 1 shows that the rhenium center is of distorted octahedral environment, consisting of five chloride atoms and one pyridine ligand. The solid-state magnetic measurements show antiferromagnetic interactions with T (Néel) of 5.5 K.

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Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

Dmitriev

Gritsan

2019

Int J of Quantum Chemistry

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The dioxolene type ligands (Diox) derived from ortho-quinones are the most widely studied redox noninnocent ligands existing in the dianionic (Cat), anion radical (SQ) or neutral (Q) forms although a highly delocalized electronic structure is also possible. For [ReO(Diox) 2 PPh 3 ] − (2) and [ReCl 3 (Diox)PPh 3 ] (3) complexes, the Re V -Cat 2 and Re IV -SQ localized valence states were proposed on the basis of their XRD structures. To understand in detail the electronic structure of these complexes, we performed a series of the all-electron calculations at the DKH2-CASSCF/CASPT2 and DKH2-CASSCF/NEVPT2 levels taking into account scalar relativistic and spin-orbit effects. All calculations predicted that 2 has a singlet ground state with a predominant contribution of a single electronic configuration with doubly occupied molecular orbitals being pure o-quinone LUMOs of both Diox ligands that corresponds to the Re V -Cat 2 valence state. Complex 3 has a triplet ground state with four electronic configurations contributing mainly into its wavefunction and differing by the occupation of bonding and antibonding combinations of the o-quinone LUMO and rhenium d-AO with nearly equal contributions. This leads to the empirical "metrical oxidation state" of dioxolene ligand being −1 that is usually referred to the Re IV -SQ oxidation state. However, in fact, the negative charge on the Diox ligand is mainly provided by a pair of electrons on the bonding MO. The standard DFT calculations entirely fail to correctly predict the ground state multiplicity for 3. K E Y W O R D S DFT and CASSCF, dioxolene ligands, electronic structure, metrical oxidation state, rhenium complexes 1 | INTRODUCTIONIn the recent years, redox noninnocent ligands have attracted much attention in coordination and organometallic chemistry. [1,2] These are the ligands, whose oxidation state in the metal complex is ambiguous and, thus, the actual oxidation state of the metal center in such complexes may differ from the formal one. Redox noninnocent ligands can serve as reservoirs for electrons, which allows one to perform many-electron transformations of metals that are impossible under other conditions. Such complexes are very wide-spread and comprise a huge variety of metal centers: namely, from the first raw transition metals to actinides. [1][2][3][4] Among them, the transition metal complexes of redox noninnocent ligands are of particular interest because of their biological importance, [5] catalytic activity, [6] and unusual magnetic properties. [7] The number of redox noninnocent ligands is also very large and includes both the small molecular species (NO and O 2 ) and a number of chelating ligands, for example, pyridine-2,6-diimines, ortho-iminoquinones, α-diimines, amidophenolates, and so forth. [1,2] The most well-known redox

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Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

Cited by 10 publications

References 28 publications

Structural and theoretical studies of (E,E)-benzaldehyde azine and its rhenium(IV) complex

Structural and theoretical studies of (E,E)-benzaldehyde azine and its rhenium(IV) complex

Solvothermal synthesis, characterization and properties of [ReCl5(py)]− complex with T (Néel) of 5.5 K

Ab initio and density functional theory study of the electronic structure of rhenium complexes with noninnocent dioxolene ligands: Localized vs delocalized valence states

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