Synthesis with Structural and Electronic Characterization of Homoleptic Fe(II)- and Fe(III)-Fluorinated Phenolate Complexes

Cantalupo, Stefanie A.; Ferreira, Helen E.; Bataineh, Eman; King, Arthur S.; Petersen, Montana V.; Wojtasiewicz, Teresa; DiPasquale, Antonio G.; Rheingold, Arnold L.; Doerrer, Linda H.

doi:10.1021/ic2003782

Cited by 41 publications

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“…In contrast, a similar linear transit study of the known [M(OC 6 F 5 ) 4 ] 2À ions, shows that these compounds with only monodentate ligands and dihedral angles of 76.98 (Co) [19] and 80.58 (Fe), [18] are much more stable in a tetrahedral geometry than square-planar, although the square-planar [Cu(OC 6 F 5 ) 4 ] 2À is also known. [19] In the absence of the chelate rings, four electronically similar donor groups give quite a distinct result.…”

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confidence: 98%

“…, M = Fe, [18] in which OAr = OC 6 F 5 or 3,5-OC 6 [22] Ni. [20] Spectroscopic [20] and computational [18] work have shown that these fluorinated ligands are medium field ligands, on par with OH À and F À , and stronger than NCO À .…”

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confidence: 99%

“…The average O-Co-O angle bridged by the enediolate ligand is 86.59(4)8, with the Na + bridged O-Co-O angle of 93.41(4)8. A molecular high-spin, square-planar {FeO 4 } compound, B, [15,45] as well as an extended lattice, solid-state example [46] of highspin, square-planar {CoO 4 2À anion, t 4 = 0.76, [18] exhibits no more distortion from T d geometry than the non-Jahn-Teller d 7 [Co(OC 6 F 5 ) 4 ] 2À , t 4 = 0.79, [19] or the d 8 [Ni(OC 6 F 5 ) 4 ] 2À , t 4 = 0.74. [20] Notably, the [Cu(OC 6 F 5 ) 4 ] 2À ion [19] exhibits rigorously planar {CuO 4 theory [47] ) were undertaken to understand why both an oxide lattice in C and diolate ligand in B could support the highspin, square-planar configuration, but not the diolate in A.…”

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confidence: 99%

“…[20] Spectroscopic [20] and computational [18] work have shown that these fluorinated ligands are medium field ligands, on par with OH À and F À , and stronger than NCO À . The electron-withdrawing power of extensively fluorinated ligands reduces the p-donor character of the O atom, such that bridging is not observed and mononuclear species are readily prepared.…”

mentioning

confidence: 99%

“…We have extensively investigated the high-spin aryloxide compounds [M(OAr) 4 ] 2À , M = Fe, [18] Co, [19] Ni, [20] and Cu [19,21] and [M(OAr) 5 ]…”

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High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure

et al. 2011

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More than half a century of intense investigation in coordination compounds has laid a firm foundation for our understanding of the ligand fields in transition-metal complexes. [1] Complexes of the heavier 4d and 5d metals are generally low spin, whereas the spin of 3d metal complexes can be high or low, depending on ligand characteristics. The number and type of donor atoms, ligand substituents, and the presence or absence of chelate rings all influence metal spin states. A combination of data-mining and detailed computational study have quantified recently these empirical observations. [2,3] In spite of such variety, there are still some types of metal complexes that are rarely observed.The stereospinomers [3] of high-spin, square-planar complexes, for example, are extremely rare because the large separation of the d [7] is known whose high-spin examples are subtly dependent on ligand substitution. Until the structure was confirmed [8] as tetrameric with octahedral coordination at the Co center, [Co(acac) 2 ] was postulated to have square-planar geometry based on magnetic and spectroscopic data that differed from tetrahedral complexes.[9] A search of the Cambridge Structural Database (V 5.32) [10] [22] Ni. [20] Spectroscopic [20] and computational [18] work have shown that these fluorinated ligands are medium field ligands, on par with OH À and F À , and stronger than NCO À . The electron-withdrawing power of extensively fluorinated ligands reduces the p-donor character of the O atom, such that bridging is not observed and mononuclear species are readily prepared.More recently, we have begun studies of the chelating perfluoropinacolate ligand, ddfp 2À . [23] Magnetic susceptibility and elemental analysis data were reported for K 2 [M(ddfp) 2 ], (M = Mn, Ni, Cu) for which square-planar geometry was proposed.[24] An octahedral bis-H 2 O adduct, (Me 4 N) 2 [Co-(OH 2 ) 2 (ddfp) 2 ] has been proposed based on elemental analysis data. [25] Despite the relative ease in making the [M(ddfp) 2 ] 2À complexes with first-row transition metals, no examples of M = Co II or Fe II have been published. We now report a highspin, square-planar Co II complex, {K(DME) 2 } 2 [Co(ddfp) 2 ] (1), and the analogous high-spin, square-planar Fe II complex {K(DME) 2 } 2 [Fe(ddfp) 2 ] (2). We also provide a discussion of three other square-planar {MO 4 } species from the recent literature whose composition and spin-state characteristics clarify the ligand requirements for the highly unusual highspin, square-planar combination in late row 3d metals.Compound 1 has been prepared as pale pink crystals as shown in Equation (1), and is stable in an inert atmosphere and in various organic solvents, but yields a brown oil upon prolonged exposure to air. Iron-containing 2, and the Zn II derivative, {K(DME) 2 } 2 [Zn(ddfp) 2 ] (3), were similarly prepared as purple-pink, and colorless crystals, respectively. No

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confidence: 98%

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confidence: 99%

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confidence: 99%

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confidence: 99%

“…We have extensively investigated the high-spin aryloxide compounds [M(OAr) 4 ] 2À , M = Fe, [18] Co, [19] Ni, [20] and Cu [19,21] and [M(OAr) 5 ]…”

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High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure

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Biological and Biomedical Aspects of Metal Phenolates

Ming

2014

Patai's Chemistry of Functional Groups

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The phenol functionality is involved in diverse biological processes and functions, serving as a proton donor and as a metal‐binding ligand. It is commonly found in many biochemicals (such as siderophores and the amino acids tyrosine and tryptophan), pharmaceuticals (including antibiotics, metal‐chelating agents, and diagnostic agents), and natural products (such as polyphenols, flavonoids, and salicylic acid). In association with other functional groups, the phenol moiety forms various types of metal‐binding sites of diverse structures and functions, for example, for iron binding and transport, in enzymes for oxygenation of substrates, and for biotransformation of aromatic compounds. Many environmentally hazardous aromatic compounds such as bisphenol A, PCB, and DDT can be degraded by tyrosinate(phenolate)‐containing metalloenzymes from microorganisms, which provides a clue for bioremediation of these toxic substances. Moreover, the phenol‐containing wet‐adhesive byssal proteins from some clams and mussels has stimulated further development of adhesive materials for medical and other applications; and the study of binding of transferrin with nanoparticles affords better understanding of protein–mineral interfacial interactions. In addition to these naturally occurring metal‐phenolate centers, there are many metal complexes of phenol and derivatives that exhibit various catalytic activities and serve as structural and/or functional model systems for tyrosinate‐containing metalloproteins.

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Coordination Chemistry of Metal Phenolates—General Aspects

Doerrer

2014

Patai's Chemistry of Functional Groups

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An overview of metal phenolate chemistry is given that highlights the structural and functional diversity of contemporary chemistry between metals from all parts of the periodic table and aryloxide ligands. After a brief overview of synthetic methods, the review is organized using structural characterization, but is not exclusive of non‐structurally characterized species. Monodentate and polydentate ligands are described and organized by the type and number of donor atoms. Within each section, the chemistry is further subdivided by the periodic table s‐, p‐, d‐, and f‐blocks. Extensive references to the literature are provided for the interested reader.

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Synthesis with Structural and Electronic Characterization of Homoleptic Fe(II)- and Fe(III)-Fluorinated Phenolate Complexes

Cited by 41 publications

References 54 publications

High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure

High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure

Biological and Biomedical Aspects of Metal Phenolates

Coordination Chemistry of Metal Phenolates—General Aspects

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Synthesis with Structural and Electronic Characterization of Homoleptic Fe(II)- and Fe(III)-Fluorinated Phenolate Complexes

Cited by 41 publications

References 54 publications

High‐Spin Square‐Planar CoII and FeII Complexes and Reasons for Their Electronic Structure

High‐Spin Square‐Planar CoII and FeII Complexes and Reasons for Their Electronic Structure

Biological and Biomedical Aspects of Metal Phenolates

Coordination Chemistry of Metal Phenolates—General Aspects

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Product

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High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure

High‐Spin Square‐Planar Co^II and Fe^II Complexes and Reasons for Their Electronic Structure