Neutral and anionic transition metal complexes supported by decafluorodiphenylamido ligands: X-ray crystal structures of {Na(THF)2}{Ti[N(C6F5)2]4}, {K(η6-C6H5Me)2}{ZrCl2[N(C6F5)2]3}, K{VCl[N(C6F5)2]3}, Fe[N(C6F5)2]2(THF)2 and Co[N(C6F5)2]2(py)2

Giesbrecht, Garth R.; Gordon, John C.; Clark, David L.; Hijar, C. A.; Scott, Brian L.; Watkin, John G.

doi:10.1016/s0277-5387(02)01258-5

Cited by 16 publications

(15 citation statements)

References 76 publications

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“…Giesbrecht and coworkers [19] have studied the compound {K(η 6 14incorporating decafluorodiphenylamido ligands. The 19 F NMR spectrum of 14 reveals pentafluorophenyl resonances in a 2:1 ratio, consistent with a trigonal bipyramidal structure being maintained in solution.…”

Section: Fig 9 Selected Bond Lengths (å) and Angles (°) In The Metamentioning

confidence: 99%

“…2.539(2)Å), and so are the Sc-benzyl (2.195(3)Å, precursor: 2.288(2)Å) and Sc-amino (2.300(3)Å, precursor: 2.470(2)Å) bond distances. In a C 6 D 5 Cl solution, the four C 6 F 5 groups in 3 showed one set of 19 F NMR signals, suggesting that it is a highly fluxional molecule, possibly due to the rapid dissociation and re-coordination of the (B(C 6 F 5 ) 4 )unit or a solvent molecule. This fluxionality was not fixed even at -45 °C, as found in a variable-temperature 19 F NMR study.…”

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confidence: 99%

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Cyclic C-F-Metal Containig Species. Solid State and Computational Examples

Carranza

Miquel

2017

J. Mex. Chem. Soc.

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<p>This article examines the results of research published between 2000 and 2012, which found experimental evidence of cyclic species containing the fragment carbon-fluorine-transition metal. 25 Examples (numbered throughout this paper) with 20 different metals and a wide variety of chemical environments have been gathered. A similar analysis brings together almost 40 transitional states and intermediates resulting from theoretical work studying the transition metal mediated carbon-fluorine bond activation. Among other aspects, this review is useful to recognize the specific characteristics which determine whether the C-F activation process is carried out through a concerted process, a mechanism assisted by auxiliary ligands or by free radicals.</p>

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Section: Fig 9 Selected Bond Lengths (å) and Angles (°) In The Metamentioning

confidence: 99%

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confidence: 99%

Cyclic C-F-Metal Containig Species. Solid State and Computational Examples

Carranza

Miquel

2017

J. Mex. Chem. Soc.

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“…In accord with NMR and elemental analysis data, two molecules of THF are coordinated to lithium. It is interesting to note, that recently a related vanadate K[VL 3 (Cl)] was prepared by reaction of KL with VCl 3 [13]. All compounds 1-11 were characterized by consistent 1 H, 13 C, and 19 F NMR spectra, by mass spectrometry, and CHN analyses (see Section 4).…”

Section: Synthesismentioning

confidence: 99%

“…C 6 D 6 was obtained from Deutero GmbH and dried over sodium. 1 H, 13 C, and 19 F NMR spectra were recorded on a Bruker ARX 200 spectrometer at 23 8C. Chemical shifts in the 1 H and 13 C NMR spectra are given in ppm relative to internal Me 4 Si; in 19 F NMR experiments CFCl 3 was used as an external standard.…”

Section: Starting Materials and Physical Measurementsmentioning

confidence: 99%

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Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride–dialkylamino exchange in decafluorodiphenlamino moiety

Shutov

Karlov

Harms

et al. 2009

Journal of Fluorine Chemistry

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Fluoro‐ and Perfluoralkylsulfonylpentafluoroanilides: Synthesis and Characterization of NH Acids for Weakly Coordinating Anions and Their Gas‐Phase and Solution Acidities

Kögel

Linder

Schröder

et al. 2015

Chemistry A European J

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Fluoro- and perfluoralkylsulfonyl pentafluoroanilides [HN(C6F5)(SO2X); X = F, CF3, C4F9, C8F17] are a class of imides with two different strongly electron-withdrawing substituents attached to a nitrogen atom. They are NH acids, the unsymmetrical hybrids of the well-known symmetrical bissulfonylimides and bispentafluorophenylamine. The syntheses, the structures of these perfluoroanilides, their solvates, and some selected lithium salts give rise to a structural variety beyond the symmetrical parent compounds. The acidities of representative subsets of these novel NH acids have been investigated experimentally and quantum-chemically and their gas-phase acidities (GAs) are reported, as well as the pKa values of these compounds in acetonitrile (MeCN) and DMSO solution. In quantum chemical investigations with the vertical and relaxed COSMO cluster-continuum models (vCCC/rCCC), the unusual situation is encountered that the DMSO-solvated acid Me2SO-H-N(SO2CF3)2, optimized in the gas phase (vCCC model), dissociates to Me2SO-H(+)-N(SO2CF3)2(-) during structural relaxation and full optimization with the solvation model turned on (rCCC model). This proton transfer underlines the extremely high acidity of HN(SO2CF3)2. The importance of this effect is studied computationally in DMSO and MeCN solution. Usually this effect is less pronounced in MeCN and is of higher importance in the more basic solvent DMSO. Nevertheless, the neglect of the structural relaxation upon solvation causes typical changes in the computational pKa values of 1 to 4 orders of magnitude (4-20 kJ mol(-1)). The results provide evidence that the published experimental DMSO pKa value of HN(SO2CF3)2 should rather be interpreted as the pKa of a Me2SO-H(+)-N(SO2CF3)2(-) contact ion pair.

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Neutral and anionic transition metal complexes supported by decafluorodiphenylamido ligands: X-ray crystal structures of {Na(THF)2}{Ti[N(C6F5)2]4}, {K(η6-C6H5Me)2}{ZrCl2[N(C6F5)2]3}, K{VCl[N(C6F5)2]3}, Fe[N(C6F5)2]2(THF)2 and Co[N(C6F5)2]2(py)2

Cited by 16 publications

References 76 publications

Cyclic C-F-Metal Containig Species. Solid State and Computational Examples

Cyclic C-F-Metal Containig Species. Solid State and Computational Examples

Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride–dialkylamino exchange in decafluorodiphenlamino moiety

Fluoro‐ and Perfluoralkylsulfonylpentafluoroanilides: Synthesis and Characterization of NH Acids for Weakly Coordinating Anions and Their Gas‐Phase and Solution Acidities

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