Tetrakis(Acetonitrile)Copper(1+) Hexafluorophosphate(1‐)

Kubas, Gregory J.; Monzyk, Br̀uce; Crumblis, A. L.

doi:10.1002/9780470132593.ch15

Cited by 232 publications

(69 citation statements)

References 5 publications

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“…Ferrocenium hexafluorophosphate (97 %, Sigma–Aldrich) was used as purchased. The salts Cu(OTf), Cu(PF 6 ), Cu(ClO 4 ), Cu(BF 4 ) and Cu(OTf) 2 were synthesised according to published procedures. The ligand DMEGqu was prepared according to a literature procedure …”

Section: Methodsmentioning

confidence: 99%

Implications of Guanidine Substitution on Copper Complexes as Entatic‐State Models

et al. 2016

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The guanidine–quinoline ligand dimethylethyleneguanidinoquinoline (DMEGqu) is able to stabilise bis(chelate) copper complexes in an intermediate geometry between tetrahedral and square‐planar environments. The structures of the obtained complexes model the entatic state and have been investigated in solid state by single‐crystal X‐ray diffraction and in the solid state and in solution by X‐ray absorption spectroscopy. The dimethylethyleneguanidine (DMEG) unit of the DMEGqu ligand displays a smaller steric encumbrance than the tetramethylguanidine (TMG) counterpart; this allows slightly larger structural changes upon oxidation than those for the TMG counterparts. Moreover, triflate coordination was possible for the CuII DMEG complexes. DFT analyses revealed that good structural and optical descriptions are possible through the use of the hybrid functionals B3LYP and TPSSh in combination with the triple‐zeta basis set def2‐TZVP and the inclusion of empirical dispersion with Becke–Johnson damping and a suitable solvent model. The orbital analysis gives insights into the electronic structure of the complexes and their charge‐transfer behaviour.

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Section: Methodsmentioning

confidence: 99%

Implications of Guanidine Substitution on Copper Complexes as Entatic‐State Models

et al. 2016

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“…Dioxygen 4.5 (99.995 %) was from Linde; isotopically enriched dioxygen‐18 ( 18 O 2 ) was from Campro Scientific and was of 99.7 % purity with the isotopic composition 18 O/ 17 O/ 16 O of 97.1:0.9:2.0 atom‐%. Tetrakis(acetonitrile)copper(I) hexafluorophosphate, [Cu(MeCN) 4 ](PF 6 ), was synthesised by following a reported method 67. The ligands R,H BOX‐Me 2 (R = H, Me, t Bu) were prepared by following the procedures we reported recently 35…”

Section: Methodsmentioning

confidence: 99%

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

et al. 2014

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The μ‐η2:η2‐peroxodicopper(II) core found in the oxy forms of the active sites of type III dicopper proteins have been a key target for bioinorganic model studies. Here, it is shown that simple bis(oxazoline)s (BOXs), which are classified among the so‐called “privileged ligands”, provide a suitable scaffold for supporting such biomimetic copper/dioxygen chemistry. Three derivatives R,HBOX‐Me2 (R = H, Me, tBu) with different backbone substituents have been used. Their bis(oxazoline)‐copper(I) complexes bind dioxygen to yield biomimetic μ‐η2:η2‐peroxodicopper(II) species. O2 can be reversibly released upon an increase in temperature. Their formation kinetics have been studied under cryo‐stopped‐flow conditions for the tBu derivative, giving activation parameters ΔH‡on = (2.27 ± 0.18) kcal mol–1, ΔS‡on = (–46.3 ± 0.8) cal K–1 mol–1 for the binding event and ΔH‡off = (11.7 ± 1.9) kcal mol–1, ΔS‡off = (–16.1 ± 8.2) cal K–1 mol–1 for the release of O2, as well as thermodynamic parameters ΔH° = (–10.0 ± 1.7) kcal mol–1 and ΔS° = (–32.7 ± 7.4) cal K–1 mol–1 for this equilibrium. The μ‐η2:η2‐peroxodicopper(II) complexes have been isolated as surprisingly stable solids and investigated in depth by a variety of methods, both in solution and in the solid state. Resonance Raman spectroscopy revealed a characteristic isotope‐sensitive stretch $\tilde {\nu}$O–O = 731–742 cm–1 (Δ[18O2] ≈ –39 cm–1) and an intense feature around 280 cm–1 diagnostic for the fundamental symmetric Cu2O2 core vibration. A slight butterfly‐shape of the Cu2O2 core has been derived from EXAFS data and DFT calculations. SQUID magnetic data evidenced strong antiferromagnetic coupled CuII2 (–2J ≥ 1000 cm–1). Thermal degradation in solution yields bis(hydroxo)‐bridged [(tBu,HBOX‐Me2)(L)Cu(OH)]2(PF6)2 (L = H2O, MeCN or THF); whereas in the case of H,HBOX‐Me2, ligand oxygenation has been detected. Preliminary reactivity studies with the substrate 2,4‐di‐tert‐butylphenol indicate the formation of the C–C coupling product 3,3′,5,5′‐tetra‐tert‐butyl‐2,2′‐biphenol, whereas ortho‐hydroxylation was not observed. The copper(I) complex [(tBu,HBOX‐Me2)Cu(MeCN)]PF6 as well as two dicopper(II) complexes [(L)(tBu,HBOX‐Me2)Cu(OH)]2(PF6)2 have been characterised by single‐crystal X‐ray diffraction. Considering the vast number of known BOX derivatives, a rich and versatile Cu/O2 chemistry based on this platform is anticipated.

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“…THF and CH 2 Cl 2 were dried by passage through solvent-purification columns. The 1H-imidazolium salts 1 -4 [20] and [Cu(MeCN) 4 ]PF 6 were prepared according to literature procedures [21], all other chemicals are commercially available and were used as received. IR Spectra: Mattson-5000-FT-IR instrument; MeCN solns.…”

Section: Experimental Partmentioning

confidence: 99%

Synthesis, Structural Diversity, and Ligand‐Transfer Potential of (Carbene)copper(I) Complexes

Venkatachalam

Heckenroth

Neels

et al. 2009

Helvetica Chimica Acta

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tel Copper(I) complexes comprising different N-heterocyclic carbene ligands were prepared via in situ deprotonation and metallation. Depending on the wingtip groups on the carbene ligand (alkyl vs. aryl, chelating or monodentate), a variety of different structural motifs were identified, such as a trigonal planar geometry (alkyl wingtips) and an unprecedented see-saw-type structure (pyridinyl wingtip groups). While aryl wingtip groups increase the stability of the complexes, alkyl substituents induce rapid demetallation in the presence of moisture. The reactivity of these complexes was used to establish a carbene-transfer protocol, which is illustrated by the formation of new cyclic thiourea compounds (transfer to sulfur) and new (carbene)ruthenium(II) complexes (transfer to ruthenium). This suggests that (carbene)copper(I) complexes could become valuable alternatives to (carbene)silver(I) complexes for synthesizing (carbene)metal systems via transmetallation.

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Tetrakis(Acetonitrile)Copper(1+) Hexafluorophosphate(1‐)

Cited by 232 publications

References 5 publications

Implications of Guanidine Substitution on Copper Complexes as Entatic‐State Models

Implications of Guanidine Substitution on Copper Complexes as Entatic‐State Models

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

Synthesis, Structural Diversity, and Ligand‐Transfer Potential of (Carbene)copper(I) Complexes

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