Bis(pyrazol-1-yl)acetates as Tripodal Heteroscorpionate Ligands in Iron Chemistry:  Syntheses and Structures of Iron(II) and Iron(III) Complexes with bpza, bdmpza, and bd<i>t</i>bpza Ligands

Beck, Alexander; Barth, Alexander; Hübner, Eike G.; Burzlaff, Nicolai

doi:10.1021/ic034097c

Cited by 89 publications

(89 citation statements)

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“…[1,[6][7][8][9][10][11][12][13][14][15][16][17] Highly active and selective catalysts for the epoxidation of olefins with turnover numbers over 120 and high stereoselectivity (97 % ee) [18] been described. [10,[19][20][21][22][23][24][25] Most of these complexes are structurally distinct from the typical non-heme enzyme active site in the sense that these lack a carboxylate, or in general an Odonor moiety and that the N-donors often stem from a pyridine ring instead of imidazole rings.…”

Section: Introductionmentioning

confidence: 99%

Mimicry of the 2‐His‐1‐Carboxylate Facial Triad Using Bulky N,N,O‐Ligands: Non‐Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co‐Ligands

et al. 2016

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Section: Introductionmentioning

confidence: 99%

Mimicry of the 2‐His‐1‐Carboxylate Facial Triad Using Bulky N,N,O‐Ligands: Non‐Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co‐Ligands

et al. 2016

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“…[5,6,9,10] The N,N,O binding motif is of particular interest not only as tripodal ligand in organometallic and coordination chemistry but as mimic of the active site of enzymes with a 2-His-1-carboxylate motif as well. [6,[11][12][13] Transition metal complexes of Hbdmpza with zinc and iron have proven to be good structural mimics for such metalloenzymes. [6,12] Due to their binding behaviour was evidenced by IR spectra of the polymer supported transition metal complexes and the uptake of manganese was proven by AAS measurements.…”

Section: Introductionmentioning

confidence: 99%

“…[6,[11][12][13] Transition metal complexes of Hbdmpza with zinc and iron have proven to be good structural mimics for such metalloenzymes. [6,12] Due to their binding behaviour was evidenced by IR spectra of the polymer supported transition metal complexes and the uptake of manganese was proven by AAS measurements. Reaction of the soluble deprotonated solid phase P1a with copper(II) chloride led to a deep-blue solid phase (P-Cu-I).…”

Section: Introductionmentioning

confidence: 99%

“…Scheme 1. The formation of bisligand complexes has been successfully prevented by the introduction of sterically more demanding substituents, such as tert-butyl, at the pyrazole rings as we reported on before. [6,12] This results in just one bound N,N,O ligand and various other ligands bound to the remaining free coordination sites. Nevertheless, this concept has not been extended to all bio-relevant transition metals, such as copper, so far, or leads to binuclear complexes.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, an influence of the sterically demanding substituents on the reactivity of the transition metal centre cannot be precluded. [12] Recently, we have been successful in introducing linking groups such as allyl and hydroxymethyl to the bridging carbon atom of 1 suitable for solid-phase fixation of bis(3,5-dimethylpyrazol-1-yl)acids and manganese and rhenium tricarbonyl complexes thereof. [15] Solid-phase-grafted ligands are not only of interest due to the advantages of supported catalysts in potential applications, [16][17][18][19] but to prevent the formation of bisligand complexes without the need of sterically demanding substituents, as well.…”

Section: Introductionmentioning

confidence: 99%

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Novel N,N,O Scorpionate Ligands and Transition Metal Complexes Thereof Suitable for Polymerisation

et al. 2008

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Esterification of 2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)‐3‐hydroxypropionic acid (2) with methacryloyl chloride led to the new κ3‐N,N,O ligand 2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)‐3‐methacrylato‐propionic acid (Hbdmpzmp) (3). The κ3‐N,N,O coordination as known from bis(3,5‐dimethylpyrazol‐1‐yl)acetic acid (Hbdmpza, 1) was proven by syntheses of the complexes [Mn(bdmpzmp)(CO)3] (4) and [Re(bdmpzmp)(CO)3] (5) and the single‐crystal X‐ray structure of 4. The methacrylic ester functionality makes 3, 4 and 5 suitable for polymerisation. Thus, copolymerisation of 3 with methyl methacrylate (MMA), a combination of MMA and ethylene glycol dimethacrylate (EGDMA) or pure EGDMA led to various solid phases (P1a–P1c, P2, P3a, P3b) with incorporated ligand. Polymer‐bound manganese and rhenium tricarbonyl complexes could be obtained by copolymerisation of 4 and 5 with MMA as well as by a polymer analogous reaction of P1a with appropriate metal salts. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymer supported transition metal complexes and the uptake of manganese was proven by AAS measurements. Reaction of the soluble deprotonated solid phase P1a with copper(II) chloride led to a deep‐blue solid phase (P‐Cu‐I). The UV/Vis absorption maximum at 715 nm indicates the copper centres to act as crosslinking agent by a similar binding behaviour as in [Cu(bdmpza)2]. In contrast, the heterogeneous reaction of P1b with copper(II) chloride formed a lime‐green solid phase (P‐Cu‐II). The bathochromic shift of the absorption maximum by 78 nm suggests one‐sided bound copper centres. EPR spectra do not show exchange narrowing between the copper centres indicating the metal centres to be far enough apart from each other to prevent magnetic interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Iron Catalysis in Biological and Biomimetic Reactions

Müller

Bröring

2008

Iron Catalysis in Organic Chemistry

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Bis(pyrazol-1-yl)acetates as Tripodal Heteroscorpionate Ligands in Iron Chemistry: Syntheses and Structures of Iron(II) and Iron(III) Complexes with bpza, bdmpza, and bdtbpza Ligands

Cited by 89 publications

References 44 publications

Mimicry of the 2‐His‐1‐Carboxylate Facial Triad Using Bulky N,N,O‐Ligands: Non‐Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co‐Ligands

Mimicry of the 2‐His‐1‐Carboxylate Facial Triad Using Bulky N,N,O‐Ligands: Non‐Heme Iron Complexes Featuring a Single Facial Ligand and Easily Exchangeable Co‐Ligands

Novel N,N,O Scorpionate Ligands and Transition Metal Complexes Thereof Suitable for Polymerisation

Iron Catalysis in Biological and Biomimetic Reactions

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