Stabilisation of a Highly Reactive Bis(μ‐oxo)dicopper(III) Species at Room Temperature by Electronic and Steric Constraint of an Unconventional Nitrogen Donor Ligand

Herres‐Pawlis, Sonja; Binder, Stephan; Eich, Andreas; Haase, Roxana; Schulz, Benjamin; Wellenreuther, Gerd; Henkel, Gerald; Rübhausen, Michael; Meyer‐Klaucke, Wolfram

doi:10.1002/chem.200901092

Cited by 45 publications

(23 citation statements)

References 41 publications

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“…They show a great accordance with the experimental data in Table . Compared to that of the Cu I complexes, the Cu–N bond lengths are significantly shortened but in the expected range for (guanidine)Cu 2 O 2 complexes , . Furthermore, the Raman modes are calculated by DFT.…”

Section: Resultsmentioning

confidence: 98%

“…An extremely stabile Cu 2 O 2 species, based on a sterically highly demanding bis(guanidine) ligand system, was synthesised and analysed accordingly. The intermediate species was stable for several days, and the structure was evaluated by a combination of Raman spectroscopy and extended X‐ray absorption fine structure (EXAFS) . Usually, the formation of bis(guanidine)–Cu 2 O 2 species is very fast and occurs within several seconds, even at temperatures of 193 K, but the Cu 2 O 2 species is then relatively stable at low temperatures.…”

Section: Introductionmentioning

confidence: 99%

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Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

et al. 2017

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Combining the new aromatic bis(guanidine) ligand bis(tetramethylguanidino)toluene (TMG2tol) and different copper salts led to four new complexes. The molecular structures were analysed by X‐ray diffraction. Three of the complexes are active in biomimetic activation of oxygen. It is the first time a bis‐µ‐oxido species of an aromatic guanidine copper complex is analysed by Raman and UV/Vis spectroscopy. The formation and decay of the bis(µ‐oxido)dicopper species were investigated at low temperatures up to 273 K by UV/Vis spectroscopy with a stopped‐flow setup. The results showed that the Cu2O2 intermediate of an aromatic guanidine–copper complex decays much faster than most known bis(guanidine) complexes. Moreover, natural bond orbital (NBO) analyses revealed that the aromatic guanidine is the stronger donor compared to the aliphatic one.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

et al. 2017

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“…The donor properties can be tuned through the choice of guanidine substituents, amine and spacers. These ligands have already been intensely investigated in bioinorganic coordination chemistry [12][13][14][15][16][17][18], but also in the ATRP of styrene [19][20][21][22][23][24]. In all of these studies, it appeared that the polyfunctional guanidines support the oxidation state change from Cu(I) over Cu(II) to Cu(III) and stabilize the corresponding complexes excellently.…”

Section: Introductionmentioning

confidence: 99%

New Guanidine-Pyridine Copper Complexes and Their Application in ATRP

et al. 2014

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Abstract:The guanidine hybrid ligands, (tetramethylguanidine)methylenepyridine (TMGpy) and (dimethylethyleneguanidine)methylenepyridine (DMEGpy), were proven to be able to stabilize copper complexes active in the solvent-free polymerization of styrene at 110 °C using 1-phenylethylbromide as the initiator. The polymerization proceeded after first-order kinetics, and polystyrenes with polydispersities around 1.2 could be obtained. Using the ligand, DMEGpy, three new copper guanidine-pyridine complexes could be synthesized and structurally characterized. Their structural characteristics are discussed.

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“…8, Table 6) [26]. When the substituents at the guanidine are [42]. By combining resonance Raman and XAS spectroscopy, it was possible to characterise the optically excited state of the bis (μ-oxo)dicopper(III) complex: owing to the large substituents, only 10% of structural distortion on the way to a peroxo core is achieved.…”

Section: Bis(guanidines)mentioning

confidence: 99%

Guanidine Metal Complexes for Bioinorganic Chemistry and Polymerisation Catalysis

Stanek

Rösener

Metz

et al. 2015

Topics in Heterocyclic Chemistry

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Guanidines are highly useful ligands which have conquered coordination chemistry within the last 20 years. Their CN 3 moiety allows multiple substitution patterns which enables tailoring them to a large variety of applications, ranging from bioinorganic coordination chemistry via medicinal chemistry to polymerisation catalysis. In bioinorganic chemistry, guanidines gave important stimuli in the modelling of copper type 1, 2 and 3 enzymes. This review provides with a comprehensive overview on complexes which have been reported with neutral guanidine ligands. Peralkylated guanidines as well as bicyclic or more complex guanidine-comprising entities are described in their coordination chemistry with transition and main-group metals. The structural features of the complexes as well as their most prominent features in bioinorganic chemistry or polymerisation catalysis are highlighted. Hereby, the role of the delocalisation of the positive charge within the guanidine unit gained during coordination is discussed in its importance for efficient and robust coordination. The delocalisation within the CN 3 unit can be measured by the structural value ρ which is discussed for numerous systems. The charge delocalisation makes neutral guanidines versatile and efficient for the stabilisation of highly different coordination modes and a large variety of oxidation states.

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Stabilisation of a Highly Reactive Bis(μ‐oxo)dicopper(III) Species at Room Temperature by Electronic and Steric Constraint of an Unconventional Nitrogen Donor Ligand

Cited by 45 publications

References 41 publications

Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

New Guanidine-Pyridine Copper Complexes and Their Application in ATRP

Guanidine Metal Complexes for Bioinorganic Chemistry and Polymerisation Catalysis

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