On the Way to a Trisanionic {Cu<sub>3</sub>O<sub>2</sub>} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands

Hannigan, Steven F.; Arnoff, Amanda I.; Neville, Sarah Elizabeth; Lum, June S.; Golen, James A.; Rheingold, Arnold L.; Orth, Nicole; Liebhäuser, Patricia; Rösener, Thomas; Stanek, Julia; Hoffmann, Alexander; Herres‐Pawlis, Sonja; Doerrer, Linda H.

doi:10.1002/chem.201605926

Cited by 15 publications

(8 citation statements)

References 90 publications

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“…Bulky alkoxides are becoming increasingly used as ancillary ligands in group-transfer chemistry and catalysis (Brazeau & Doerrer, 2019;Chua & Duong, 2014;Hannigan et al, 2017;Jayasundara et al, 2018;Wannipurage et al, 2020). As a result of their stereoelectronic properties, profoundly weak-field bulky alkoxides enable formation of reactive low-coordinate high-spin middle and late transition-metal centers (Bellow et al, 2016b;Grass et al, 2019b).…”

Section: Chemical Contextmentioning

confidence: 99%

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Kurup¹,

Nasser²,

Ward³

et al. 2022

Acta Cryst E

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A new sterically bulky chelating bis(alkoxide) ligand 3,3′-([1,1′:4′,1′′-terphenyl]-2,2′′-diyl)bis(2,2,4,4-tetramethylpentan-3-ol), (H2[OO]tBu), was prepared in a two-step process as the dichloromethane monosolvate, C36H50O2·CH2Cl2. The first step is a Suzuki–Miyaura coupling reaction between 2-bromophenylboronic acid and 1,4-diiodobenzene. The resulting 2,2′′-dibromo-1,1′:4′,1′′-terphenyl was reacted with t BuLi and hexamethylacetone to obtain the desired product. The crystal structure of H2[OO]tBu revealed an anti conformation of the [CPh2(OH)] fragments relative to the central phenyl. Furthermore, the hydroxyl groups point away from each other. Likely because of this anti–anti conformation, the attempts to synthesize first-row transition-metal complexes with H2[OO]tBu were not successful.

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Section: Chemical Contextmentioning

confidence: 99%

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Kurup¹,

Nasser²,

Ward³

et al. 2022

Acta Cryst E

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“…55 The absorption spectra were modeled with quasidegenerate perturbation theory on top of strongly contracted nelectron valence perturbation theory applied to state-averaged complete-active-space self-consistent-field wave functions (QDPT +NEVPT2/SA-CASSCF), 56 which has been successfully applied to Ln III systems by Neese et al 53,57 The active space for the SA-CASSCF calculations included 3/6/9 electrons correlated with seven f orbitals for the Nd/Eu/Dy species. For the Nd species (1-Nd and 3-Nd), the active space was averaged over the full set of states derived from the free-ion terms (35 quartet and 112 doublet [QDPT+SA (35,112)-NEVPT2(3,7)]) for a complete intermediate coupling treatment. For the Eu species (2-Eu and 4-Eu), the active space was averaged over the states derived from the full set of septet and quintet free-ion states, and triplet states derived from the 3 P, 3 O, 3 M, 3 K, 3 H, 3 F, and 3 I freeion states (7 septet, 140 quintet, and 91 triplet [QDPT+SA- (7,140,91)-NEVPT2(6,7)]).…”

Section: Esi-ms Calcd For {mentioning

confidence: 99%

“…Our group has previously used fluorinated alkoxides and aryloxides to produce a family of complexes including an unusual trivalent Cu species, three-coordinate transition-metal complexes in exclusively O-donor environments, and rare high-spin square-planar metal centers. , To date, five 3d metals (Fe, − Co, , Ni, Cu, ,,,− and Zn , ) have been prepared as homonuclear, homoleptic [M(pin F ) 2 ] 2– and [M(OC 4 F 9 ) n ] m − complexes, heteroleptic [(R 3 P) 2 M(OR F ) 2 ] complexes, and main-group species Tl(OC 4 F 9 ) . Thus, with the goal of preparing luminescent Ln III complexes with fluorinated alkoxide ligands and homoleptic O-donor environments, we undertook the synthesis and characterization of a series of Ln III complexes, whose syntheses are shown in Scheme , with [OC 4 F 9 ] − ligands, and in Scheme for [pin F ] 2– (perfluoropinacolate) ligands.…”

Section: Introductionmentioning

confidence: 99%

Luminescence of Lanthanide Complexes with Perfluorinated Alkoxide Ligands

et al. 2020

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Four groups of rare-earth complexes, comprising 11 new compounds, with fluorinated O-donor ligands ([K(THF)6][Ln(OC4F9)4(THF)2] (1-Ln; Ln = Ce, Nd), [K](THF) x [Ln(OC4F9)4(THF) y ] (2-Ln; Ln = Eu, Gd, Dy), [K(THF)2][Ln(pinF)2(THF)3] (3-Ln; Ln = Ce, Nd), and [K(THF)2][Ln(pinF)2(THF)2] (4-Ln; Ln = Eu, Gd, Dy, Y) have been synthesized and characterized. Single-crystal X-ray diffraction data were collected for all compounds except 2-Ln. Species 1-Ln, 3-Ln, and 4-Ln are uncommon examples of six-coordinate (Eu, Gd, Dy, and Y) and seven-coordinate (Ce and Nd) LnIII centers in all-O-donor environments. Species 1-Ln, 2-Ln, 3-Ln, and 4-Ln are all luminescent (except where Ln = Gd and Y), with the solid-state emission of 1-Ce being exceptionally blue-shifted for a Ce complex. The emission spectra of the six Nd, Eu, and Dy complexes do not show large differences based on the ligand and are generally consistent with the well-known free-ion spectra. Time-dependent density functional theory results show that 1-Ce and 3-Ce undergo allowed 5f → 4d excitations, consistent with luminescence lifetime measurements in the nanosecond range. Eu-containing 2-Eu and 4-Eu, however, were found to have luminescence lifetimes in the millisecond range, indicating phosphorescence rather than fluorescence. The performance of a pair of multireference models for prediction of the Ln = Nd, Eu, and Dy absorption spectra was assessed. It was found that spectroscopy-oriented configuration interaction as applied to a simplified model in which the free-ion lanthanide was embedded in ligand-centered Löwdin point charges performed as well (Nd) or better (Eu and Dy) than canonical NEVPT2 calculations, when the ligand orbitals were included in the treatment.

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“…Polynuclear oxo or hydroxy bridged copper units are also found in multicopper oxidases [ 24 , 38 , 39 , 40 , 41 ], but only a few examples of the proposed Cu n O m active sites are thought to contain μ 3 -oxo or μ 3 -hydroxy bridged trinuclear units similar to the types which are formed oxime ligands listed in Figure 3 and Figure 5 which are the subject of this paper [ 42 , 43 ].…”

Section: Introductionmentioning

confidence: 99%

From Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes

et al. 2022

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Conditions have been identified in which phenolic aldoximes and ketoximes of the types used in commercial solvent extraction processes can be doubly deprotonated and generate polynuclear Cu complexes with lower extractant:Cu molar ratios than those found in commercial operations. Electrospray mass spectrometry has provided an insight into the solution speciation in extraction experiments and has identified conditions to allow isolation and characterization of polynuclear Cu-complexes. Elevation of pH is effective in enhancing the formation of trinuclear complexes containing planar {Cu3-μ3-O}4+ or {Cu3-μ3-OH}5+ units. DFT calculations suggest that such trinuclear complexes are more stable than other polynuclear species. Solid structures of complexes formed by a salicylaldoxime with a piperidino substituent ortho to the phenolic OH group (L9H2) contain two trinuclear units in a supramolecular assembly, {[Cu3OH(L9H)3(ClO4)](ClO4)} 2, formed by H-bonding between the central {Cu3-μ3-OH}5+ units and oxygen atoms in the ligands of an adjacent complex. Whilst the lower ligand:Cu molar ratios provide more efficient Cu-loading in solvent extraction processes, the requirement to raise the pH of the aqueous phase to achieve this will make it impractical in most commercial operations because extraction will be accompanied by the precipitation (as oxyhydroxides) of Fe(III) which is present in significant quantities in feed solutions generated by acid leaching of most Cu ores.

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On the Way to a Trisanionic {Cu₃O₂} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands

Cited by 15 publications

References 90 publications

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Luminescence of Lanthanide Complexes with Perfluorinated Alkoxide Ligands

From Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes

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On the Way to a Trisanionic {Cu3O2} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands

Cited by 15 publications

References 90 publications

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Synthesis and structure of a new bulky bis(alkoxide) ligand on a terphenyl platform

Luminescence of Lanthanide Complexes with Perfluorinated Alkoxide Ligands

From Gas Phase Observations to Solid State Reality: The Identification and Isolation of Trinuclear Salicylaldoximato Copper Complexes

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Product

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On the Way to a Trisanionic {Cu₃O₂} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands