Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Ording-Wenker, Erica C.M.; Siegler, Maxime A.; Bouwman, Elisabeth

doi:10.1016/j.ica.2014.12.033

Cited by 13 publications

(22 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Two main strategies have been employed to synthesize metal fluoride compounds: the first one is based on the addition of fluoride salts like NaF or AsF3 as fluorinating agents; the other one is based on the use of metal tetrafluoridoborate as starting salts, which generate fluoride ions upon decomposition. In the last decades, tremendous efforts have been put in the synthesis of copper(II) fluoride compounds from copper tetrafluoridoborate [4][5][6][7]. Recently, Reger et al.…”

mentioning

confidence: 99%

A tetranuclear fluorido-bridged iron compound: Fluoride abstraction from the tetrafluoridoborate anion

Feng

Siegler

Bouwman

2018

Inorganic Chemistry Communications

Self Cite

View full text Add to dashboard Cite

The novel iron(II) fluoride cluster [Fe II 4(L 1 SSL 1)2F6(MeCN)2](BF4)2 (L 1 SSL 1 = di-2-(bis(2pyridylmethyl)amino)ethyl disulfide) has been synthesized by reaction of the ligand L 1 SSL 1 with [Fe(MeCN)6](BF4)2. The crystal structure shows that a tetranuclear iron(II) compound is formed through the bridging of two dinuclear iron(II) units by four fluoride anions. The 19 F NMR spectrum distinguishes both the terminal and bridging fluoride ions in this compound. The new compound is a rare Fe II fluoride cluster with four Fe II and four F − ions arranged in a nearly perfect square plane, which obtained its fluoride ions from the tetrafluoridoborate anion.

show abstract

mentioning

confidence: 99%

A tetranuclear fluorido-bridged iron compound: Fluoride abstraction from the tetrafluoridoborate anion

Feng

Siegler

Bouwman

2018

Inorganic Chemistry Communications

Self Cite

View full text Add to dashboard Cite

show abstract

“…Changing the bridge between the tertiary amine and the pyridyl groups from a methylene to an ethylene spacer at two positions leads to an increase in activity (entry 3 vs. 8), but at four positions it leads to a dramatic decrease in activity (entry 3 vs. 9). 24 which is reflected in the negative effect on the catalytic activity (entries 14 and 15). The catalytic activity decreases with increasing concentration of chloride ions, as can be seen in (Fig.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

“…15 The existence of an equilibrium between dinuclear Cu Idisulfide compounds and the redox isomeric dinuclear Cu II µ-thiolate compounds has been shown to be strongly dependent on the redox potential of these compounds, as induced by the electronic and steric properties of the ligand system. 24 Similarly, it may be argued that the high activity of the systems has been proposed to be the rate-determining step of the reaction, this will thus result in an increase of the overall reaction rate. 14,17,37 The activity of these catalytic systems can probably be increased even further by using a protic solvent like methanol, but this might also result in faster catalyst degradation.…”

Section: Paper Dalton Transactionsmentioning

confidence: 99%

Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship

et al. 2015

Self Cite

View full text Add to dashboard Cite

A large library of Cu II complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu⋯Cu distances and the formation of polymeric species. Comparison of the 3,5-DTBC oxidation rates showed that ligands that stabilize the biomimetic dinuclear Cu II µ-thiolate complex also result in copper compounds that are much more active in the oxidation of 3,5-DTBC. This oxidation activity is however inhibited by the presence of chloride ions. The highest k cat that was observed was 6900 h, which is one of the highest turnover frequencies reported so far for catechol oxidation in CH 3 CN.

show abstract

“…II displays a broad d-d transition band of weak intensity around 700 nm. 38 Because the ~364 nm absorption range is obscured by the sulfane product 1 (lmax = 375 nm) under our reaction conditions, and given the rapid ligand-exchange equilibria common with phenanthroline-ligated copper(I) species, we will use "(phen)Cu I " to refer to both the mono-and bisphenanthroline ligated copper(I) species throughout this study.…”

mentioning

confidence: 99%

“…The reaction mixture has an initial brown color and a strong absorption at 440 nm characteristic of a (phen)Cu I species (Figure 2, black trace) 37 and a broad band of weak intensity around 699 nm attributed to Cu II . 38 The presence of copper(II) in the initial reaction mixture results from background oxidation of copper(I) under these aerobic conditions. The band at 440 nm is suggestive of the formation of (phen)Cu I .…”

mentioning

confidence: 99%

Intermediacy of Copper(I) under Oxidative Conditions in the Aerobic Copper-Catalyzed Decarboxylative Thiolation of Benzoic Acids

Green

Hoover

2019

ACS Catal.

View full text Add to dashboard Cite

An experimental mechanistic study of the aerobic copper-catalyzed decarboxylative thiolation of benzoic acids with aryl thiols is reported. For the model reaction, the findings support the corresponding disulfide (PhSSPh) of the aryl thiol (PhSH) as the active thiolating source under reaction conditions. Synthesis and reactivity studies along with kinetic measurements support the chemical and kinetic competence of catalytically active welldefined Cu-complexes; (phen)Cu I (O2CC6H4-o-NO2) (2), (phen)Cu I (C6H4-o-NO2) (4), [(phen)Cu I (µ-SC6H5)]2 (3) and (phen)Cu II (O2CC6H4-o-NO2)2 (5), (phen = 1,10-phenanthroline). The presence of an induction period in the stoichiometric reaction of copper(II) complex (phen)Cu II (O2CC6H4-o-NO2)2 (5) with PhSSPh, and the absence of an induction period in the analogous stoichiometric reaction of copper(I) complex (phen)Cu I (O2CC6H4-o-NO2) (2), suggests a copper(I) carboxylate is a more likely intermediate than a copper(II) carboxylate. The observation of in situ reduction of Cu II to Cu I further supports Cu I as the primary active catalytic species and spectroscopic studies also indicate the catalyst resting state to be a Cu I species. The catalytic reaction exhibits a first order dependence on [Cu I ] and [2nitrobenzoic acid] and a zero order dependence on [PhSSPh] and pO2, suggestive of turnover limiting decarboxylation of a copper(I) carboxylate. Oxygen was found to promote the essential oxidative cleavage of the copper(I)thiolate intermediate [(phen)Cu(µ-SC6H5)]2 (3) to regenerate a catalytically active [(phen)Cu II ] (Cuox) species with concomitant formation of PhSSPh. On the basis of these findings, a reaction pathway is proposed for the C-S coupling reaction that includes the key Cu I-based intermediates, (phen)Cu(O2CC6H4-o-NO2) (2), and (phen)Cu(C6H4o-NO2) (4). The pathway accounts for the role of O2 in generating the active thiolating source, PhSSPh, as well as enabling catalytic turnover of in situ generated [(phen)Cu(µ-SC6H5)]2 (3).

show abstract

Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Cited by 13 publications

References 29 publications

A tetranuclear fluorido-bridged iron compound: Fluoride abstraction from the tetrafluoridoborate anion

A tetranuclear fluorido-bridged iron compound: Fluoride abstraction from the tetrafluoridoborate anion

Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship

Intermediacy of Copper(I) under Oxidative Conditions in the Aerobic Copper-Catalyzed Decarboxylative Thiolation of Benzoic Acids

Contact Info

Product

Resources

About