AgOC(CF<sub>3</sub>)<sub>3</sub>:  Synthesis and Applications of the First Donor-Free Silver(I) Alkoxide

Reisinger, Andreas; Trapp, and Nils; Krossing, Ingo

doi:10.1021/om061046p

Cited by 47 publications

(59 citation statements)

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“…Similar tetrameric fluorinated alkoxide structures of [LiA C H T U N G T R E N N U N G (OC 4 F 9 )] 4 [15] and [NaA C H T U N G T R E N N U N G (OC 4 F 9 )] 4 [16] have been reported previously.…”

Section: Resultssupporting

confidence: 82%

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Lum

Tahsini

Golen

et al. 2013

Chemistry A European J

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Seven E[Cu(OR)2] copper(I) complexes (E = K(+), {K(18C6)}(+) (18C6 = [18]crown-6), or Ph4P(+); R = C4F9, CPhMe(F)2, and CMeMe(F)2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 2:1 and 3:1 Cu/O2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}(+) or Ph4P(+) derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K(+) ions induce aggregation of multiple [Cu(OR)2](-) units through K⋅⋅⋅F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K(+) ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a Cu(II) carbonate has been isolated and characterized.

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Section: Resultssupporting

confidence: 82%

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Lum

Tahsini

Golen

et al. 2013

Chemistry A European J

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“…We also note that [(H 4 C 2 Ag) 3 4 ] À , the only other known [48] silver-ethene complex for which both X-ray distance (135.1 (2) , with vibrational spectroscopy. [36] Shortly after, the homologous Pd and Pt complexes were prepared [37,38] and in 1983 the crystal structure of [PtA C H T U N G T R E N N U N G (h 2 -C 2 H 4 ) 3 ] was determined.…”

Section: Wwwchemeurjorgmentioning

confidence: 71%

“…Important descriptors for the bonding in [MA C H T U N G T R E N N U N G (C 2 H 4 ) 3 ] (planar spoke wheel geometry; M = Na + , Cu + , Ag + , Au + , Ni, Pd, Pt). [35,36,40,41,88] …”

Section: A C H T U N G T R E N N U N G (C 2 H 4 ) 3 ]mentioning

confidence: 99%

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Reisinger

Trapp

Knapp

et al. 2009

Chemistry A European J

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Compounds including the free or coordinated gas-phase cations [Ag(eta(2)-C(2)H(4))(n)](+) (n = 1-3) were stabilized with very weakly coordinating anions [A](-) (A = Al{OC(CH(3))(CF(3))(2)}(4), n = 1 (1); Al{OC(H)(CF(3))(2)}(4), n = 2 (3); Al{OC(CF(3))(3)}(4), n = 3 (5); {(F(3)C)(3)CO}(3)Al-F-Al{OC(CF(3))(3)}(3), n = 3 (6)). They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of ethene in CH(2)Cl(2) solution. As a reference we also prepared the isobutene complex [(Me(2)C=CH(2))Ag(Al{OC(CH(3))(CF(3))(2)}(4))] (2). The compounds were characterized by multinuclear solution-NMR, solid-state MAS-NMR, IR and Raman spectroscopy as well as by their single crystal X-ray structures. MAS-NMR spectroscopy shows that the [Ag(eta(2)-C(2)H(4))(3)](+) cation in its [Al{OC(CF(3))(3)}(4)](-) salt exhibits time-averaged D(3h)-symmetry and freely rotates around its principal z-axis in the solid state. All routine X-ray structures (2theta(max.) < 55 degrees) converged within the 3sigma limit at C=C double bond lengths that were shorter or similar to that of free ethene. In contrast, the respective Raman active C=C stretching modes indicated red-shifts of 38 to 45 cm(-1), suggesting a slight C=C bond elongation. This mismatch is owed to residual librational motion at 100 K, the temperature of the data collection, as well as the lack of high angular data owing to the anisotropic electron distribution in the ethene molecule. Therefore, a method for the extraction of the C=C distance in [M(C(2)H(4))] complexes from experimental Raman data was developed and meaningful C=C distances were obtained. These spectroscopic C=C distances compare well to newly collected X-ray data obtained at high resolution (2theta(max.) = 100 degrees) and low temperature (100 K). To complement the experimental data as well as to obtain further insight into bond formation, the complexes with up to three ligands were studied theoretically. The calculations were performed with DFT (BP86/TZVPP, PBE0/TZVPP), MP2/TZVPP and partly CCSD(T)/AUG-cc-pVTZ methods. In most cases several isomers were considered. Additionally, [M(C(2)H(4))(3)] (M = Cu(+), Ag(+), Au(+), Ni(0), Pd(0), Pt(0), Na(+)) were investigated with AIM theory to substantiate the preference for a planar conformation and to estimate the importance of sigma donation and pi back donation. Comparing the group 10 and 11 analogues, we find that the lack of pi back bonding in the group 11 cations is almost compensated by increased sigma donation.

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“…The single crystals were mounted in perfluoroether oil on a MiTeGen Micromount TM . Dibromoborylferrocene, 1,1'-bis(dibromoboryl)ferrocene, Ag + [Al(OR F ) 4 ] -, and LiOhfip were synthesized according to the established procedures [24][25][26]33,37].…”

Section: Methodsmentioning

confidence: 99%

“…We suggest that compound 2 was formed, but that the B-C bond was cleaved by the HBr released giving ferrocene and the volatile alkoxybromoborane Br-B(Ohfip) 2 . To prevent the formation of HBr, the alcohol was replaced by the alkoxide Li[Ohfip] [37]. The consecutively generated LiBr could be removed, and the clean products 1 and 2 were obtained in good yield (71 % 1; 81 % 2) after recrystallization from hexane or CH 2 Cl 2 , respectively (eq.…”

Section: -(Bohfip 2 )Fc 1 and 11'-(bohfip 2 ) 2 Fcmentioning

confidence: 99%

Synthesis and oxidation of hexafluoroisopropoxyborylferrocenes

Böhrer

Trapp

Scherer

et al. 2012

Pure and Applied Chemistry

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AgOC(CF₃)₃: Synthesis and Applications of the First Donor-Free Silver(I) Alkoxide

Cited by 47 publications

References 50 publications

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)

Synthesis and oxidation of hexafluoroisopropoxyborylferrocenes

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AgOC(CF3)3: Synthesis and Applications of the First Donor-Free Silver(I) Alkoxide

Cited by 47 publications

References 50 publications

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Silver–Ethene Complexes [Ag(η2‐C2H4)n][Al(ORF)4] with n=1, 2, 3 (RF=Fluorine‐Substituted Group)

Synthesis and oxidation of hexafluoroisopropoxyborylferrocenes

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AgOC(CF₃)₃: Synthesis and Applications of the First Donor-Free Silver(I) Alkoxide

Silver–Ethene Complexes [Ag(η²‐C₂H₄)_n][Al(OR^F)₄] with n=1, 2, 3 (R^F=Fluorine‐Substituted Group)