Stepwise construction of mono-, di- and tri-nuclear 2 ? 1, 1 ? 2, 2 ? 3 ligand ? mixed-metal complexes using a bis-tridentate bridging ligand

Hazell, Alan; Hazell, Rita G.; McKenzie, Christine J.; Nielsen, Lars Preuss

doi:10.1039/b212624a

Cited by 11 publications

(6 citation statements)

References 12 publications

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“…It is found that TpmC* becomes κ 2 in B , C , and D (Cu‐N≈2.0 Å, Cu⋅⋅⋅N 2.5–2.6 Å) and the BF 4 − therein interacts rather strongly with Cu (Cu⋅⋅⋅F≈2.3 Å). Strong interactions between Cu and BF 4 − are precedented [43] . The calculated spin density ( ρ ) is consistent with our assignment from EPR and electronic spectroscopy.…”

Section: Resultssupporting

confidence: 87%

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site

et al. 2021

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Dianionic hyponitrite (N 2 O 2 2À)i so ften proposed, based on model complexes,asthe key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases.I n this work, we examine the gas-solid reaction of nitric oxide with the metal-organic framework Cu I-ZrTpmC* with asuite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 C À intermediate.T hese results highlight the advantage provided by site-isolation in metal-organic frameworks (MOFs) for studying important reaction intermediates,a nd provideamechanistic scenario compatible with the proposed one-electron couple in these enzymes.

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Section: Resultssupporting

confidence: 87%

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site

et al. 2021

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“…In this context, we have decided to extend this system to other rigid bridging ligands such as the tetra-N-functionalized pphenylenediamine co-ligands acting with a bis(tridentate) bridging coordination mode [14] (Scheme 1). As the 2,2'-bpym ligand, it has been clearly established that such rigid hexadentate bridging coligand, owing to its specific electronic and structural features, could be a suitable building block for the design of various co-ordination derivatives, from mononuclear to extended molecular systems [14][15][16][17]. Furthermore, such derivatives could find applications in the bioinorganic chemistry field as exemplified by the copper(II) complexes based on the 1,4-tpbd ligand (N,N,N'N'-tetrakis(2-pyridylmethyl)benzene-1,4-diamine) which have recently been investigated for their DNA cleavage properties [18][19].…”

Section: Introductionmentioning

confidence: 99%

Polypyridyl-based Cu(II) coordination polymers: Synthesis, structural and magnetic characterizations

et al. 2015

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International audienceNew Cu(II) coordination polymeric neutral chains of formula [Cu 2 (1,4-tpbd)Cl 2 L 2)] (1,4-tpbd = N,N,N'N'-tetrakis(2-pyridylmethyl)benzene-1,4-diamine, L = 1,1,3,3-tetracyano-2-ethoxypropenide (tcnoet)-(1) or 1,1,3,3-tetracyano-2-propoxypropenide (tcnopr)-(2)) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction and magnetic measurements. The crystal structure determinations of 1 and 2 reveal in both cases a one-dimensional structure in which the 1,4-tpbd acts as a bis-chelating ligand and the two chloride anions as asymmetrical bridging ligands. The Cu···Cu distances through the bis-chelating 1,4-tpbd ligand (8.194(1) and 8.245(3) Å for 1 and 2 respectively) are in the range of the corresponding distances observed for parent complexes involving similar bridges; and as expected, the Cu···Cu distances through the asymmetrical ( 2-Cl) 2 bridges are significantly shorter (4.021(2) and 4.125(2) Å for 1 and 2, respectively). For both compounds, magnetic measurements exhibit a maximum in the  m vs. T plot (at 50 K for 1, and at 48 K for 2), characteristic of antiferromagnetic exchange interactions occurring mainly through the tbpd organic ligand that can be very well reproduced with a S = ½ dimer model with g = 2.114, J =-41.2 cm-1 for 1 and g = 2.105 and J =-39.3 cm-1 for 2.

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“…7 Dipicolylamine (dpa) ligands have also seen widespread application in Cu coordination chemistry. In particular, homobimetallic systems have been used as subunits in coordination polymers [8][9][10][11][12][13][14][15] and as models for Cu metalloenzymes including methane monooxygenase and hemocyanin. [16][17][18][19][20][21][22] Karlin et al has demonstrated the flexible nature of these ligands, using derivatives in which the central amine is functionalized with aryl groups containing ortho-OMe and meta-t Bu substituents to support the oxidation of Cu I with O 2 to form μ-1,2-peroxodicopper(II) adducts.…”

Section: Introductionmentioning

confidence: 99%

Conformationally dynamic copper coordination complexes

et al. 2022

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Stepwise construction of mono-, di- and tri-nuclear 2 ? 1, 1 ? 2, 2 ? 3 ligand ? mixed-metal complexes using a bis-tridentate bridging ligand

Cited by 11 publications

References 12 publications

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF‐Supported Mononuclear Copper Site

Polypyridyl-based Cu(II) coordination polymers: Synthesis, structural and magnetic characterizations

Conformationally dynamic copper coordination complexes

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