Fluorinated phenolates in monomeric and dimeric Co(II) compounds

Petersen, Montana V.; Iqbal, Amber H.; Zakharov, Lev N.; Rheingold, Arnold L.; Doerrer, Linda H.

doi:10.1016/j.poly.2012.09.032

Cited by 11 publications

(7 citation statements)

References 18 publications

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“…28,29 Nevertheless, this value is in agreement with other reported effective magnetic moments of high-spin Co(II) complexes with formulas [CoX 4 ] 2− (X = anionic ligand), which range between 4.4 and 5.1 μ B . [24][25][26]30,31 Therefore, the [Co(OTeF 5 ) 4 ] 2− anion can be described as a d 7 system with a quartet (S = 3/2) ground state. Additionally, a simulation of the magnetic data was successfully performed, as shown in Figure 2.…”

Section: Introductionmentioning

confidence: 99%

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex

et al. 2023

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The pentafluoroorthotellurate group (teflate, OTeF 5 ) is considered as a bulky analogue of fluoride, yet its coordination behavior in transition metal complexes is not fully understood. By reaction of [CoCl 4 ] 2− and neat ClOTeF 5 , we synthesized the first cobalt teflate complex, [Co(OTeF 5 ) 4 ] 2− , which exhibits moisture-resistant Co−OTeF 5 bonds. Through a combined experimental and theoretical (DFT and NEVPT2) study, the properties and electronic structure of this species have been investigated. It exhibits a distorted tetrahedral structure around the cobalt center and can be described as a d 7 system with a quartet (S = 3/2) ground state. A comparative bonding analysis of the (pseudo)tetrahedral [CoX 4 ] 2− anions (X = OTeF 5 , F, Cl) revealed that the strength of the Co−X interaction is similar in the three cases, being the strongest in [Co(OTeF 5 ) 4 ] 2− . In addition, an analysis of the charge of the Co center reinforced the similar electronwithdrawing properties of the teflate and fluoride ligands. Therefore, the [Co(OTeF 5 ) 4 ] 2− anion constitutes an analogue of the polymeric [CoF 4 ] 2− in terms of electronic properties, but with a monomeric structure.

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Section: Introductionmentioning

confidence: 99%

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex

et al. 2023

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“…The high-spin Co(II) complexes exhibit excellent magnetic properties, which arise from the strong orbital angular momentum, such as several phenoxo-bridged cobalt(II) complexes behaving as single-molecule magnets. , Dinuclear complexes are suitable for investigating the magnetic interactions between paramagnetic centers transmitted through the phenoxo bridge because of their simple structures. , Over the past decades, a lot of reports have been made on dinuclear bis(μ-phenoxo)-bridged cobalt(II) complexes; in addition, most of them exhibit antiferromagnetic coupling (AF) between cobalt(II) centers, ,,− and only four cases show ferromagnetic coupling (F) between cobalt(II) centers. ,− To further understand the magnetic behavior of this system, more new μ-phenoxo-bridged Co(II) complexes need to be obtained and studied. Herein, we designed and synthesized a new Schiff-base ligand, (4-methyl-2-formyl-6-(((2-trifluoromethyl)phenyl)methyliminomethyl) phenol) (HL).…”

Section: Introductionmentioning

confidence: 99%

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Song

Xue

2020

ACS Omega

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A new μ-phenoxo-bridged dinuclear cobalt(II) complex, [Co2(L)2(acac)2(H2O)] (1), has been synthesized by employing a new ligand, (4-methyl-2-formyl-6-(((2-trifluoromethyl)phenyl)methyliminomethyl) phenol) (HL). Structural analysis of complex 1 reveals that the geometry around cobalt centers is best described as a distorted octahedron and the distance of cobalt neighbors is 3.128(0) Å. The magnetic property studies indicate that complex 1 exhibits strong spin–orbit coupling effects and weak ferromagnetic coupling between two high-spin Co(II) centers linked by double μ-Ophenoxo bridges, with J = 1.87(2) cm–1. The studies show that not only the Co–O–Co angle affects the alignment of the cobalt spins but also the dihedral angle between the CoOCo plane and the phenyl plane plays an important role in the magnetic coupling in this [Co2O2] system. Thus, the small bridging angles (96.96(11) and 96.91(11)°) and the large dihedral angles between the CoOCo plane and the phenyl plane (63.0(1) and 30.6(1)°) induce intramolecular ferromagnetic exchange interaction in complex 1.

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“…The Co‐SO 2 distance is slightly shorter to that reported in Co(SO 2 ) 2 [SbF 6 ] 2 [35] . Analogous compounds with non‐fluorinated alkoxides have the Co‐alkoxide distances shorter than in IVa or IVb , often in the range 1.93–1.94 Å [33,34] . This is easy to explain by higher charge density on O atoms in the absence of strongly electron withdrawing C(CF 3 ) 3 groups.…”

Section: Cobalt Compoundsmentioning

confidence: 80%

“…[35] Analogous compounds with non-fluorinated alkoxides have the Co-alkoxide distances shorter than in IVa or IVb, often in the range 1.93-1.94 Å. [33,34] This is easy to explain by higher charge density on O atoms in the absence of strongly electron withdrawing C(CF 3 ) 3 groups. Interestingly, CoÀ O bonds are longer for IVa, which is probably the result of steric crowding around the cation.…”

Section: Crystal Structuresmentioning

confidence: 99%

Stabilization of Potent Co(II)‐based Lewis Acids with Weakly Basic Ligands

Jadwiszczak

Malinowski

2022

Chemistry A European J

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Pairing cations with weakly coordinating anions (WCAs) often renders them highly Lewis-acidic and extremely reactive. Although these features are often desirable, excessive reactivity of a cation may lead to decomposition of solvents or WCAs, hindering isolation, storage and practical use of such species. In an attempt to mitigate the problem, we introduce a series of readily available novel Co(II)-WCA salts with the metal center stabilized by weakly bound ligands: SO 2 , halogenated acetonitriles and nitromethane with comprehensive characterization including structural, magnetic and spectral (IR) properties as well as thermal stability assessment. The use of these simple yet rarely encountered ligands yields mostly stable and highly Lewis-acidic com-plexes, in some cases comparable to SbF 5 according to calculated Fluoride Ion Affinities. Highly acidic character of the species is also reflected in observed reactivity. Since the most convenient route towards the Co(II) complexes leads through silver salts, the results are complemented with characterization of a series of novel Ag(I) complexes with abovementioned ligands. Experimental part is backed with DFT calculations which gives insight into the structure and energetics of presented Co(II) complexes and shows that Co(II) center is available for substrates like olefins. This makes them good candidates for catalysts in reactions requiring the presence of Lewis acids.

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Fluorinated phenolates in monomeric and dimeric Co(II) compounds

Cited by 11 publications

References 18 publications

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex

Study on the Magneto-Structural Correlation of a New Dinuclear Cobalt(II) Complex with Double μ-Phenoxo Bridges

Stabilization of Potent Co(II)‐based Lewis Acids with Weakly Basic Ligands

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