420-56-4Relevant articles and documents
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Lange,H.,Naumann,D.
, p. 309 (1985)
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Rearrangement in a Tripodal Nitroxide Ligand to Modulate the Reactivity of a Ti-F Bond
Boreen, Michael A.,Bogart, Justin A.,Carroll, Patrick J.,Schelter, Eric J.
, p. 9588 - 9593 (2015)
The tripodal nitroxide ligand [(2-tBuNO)C6H4CH2)3N]3- (TriNOx3-) binds the Ti(IV) cation and prevents inner-sphere coordination of chloride in the complex [Ti(TriNOx)]Cl (1). The ligand undergoes an η2-NO to κ1-O rearrangement to enable a fluoride ion to bind in the related complex Ti(TriNOx)F (2). Computational and reactivity studies demonstrated that the ligand rearrangement contributed to the enthalpy change in the transfer of a fluoride anion.
A Facile Preparation of Rubidium and Caesium Selenocarboxylates
Kawahara, Yasuyuki,Kato, Shinzi,Kanda, Takahiro,Murai, Toshiaki,Ishihara, Hideharu
, p. 277 - 278 (1993)
Treatment of O-trimethylsilyl selenocarboxylates with rubidium and caesium fluorides affords rubidium and ceasium selenocarboxylates in good yields.
Synthesis and characterization of (2,6-difluorophenyl)xenone(II) and bis(2,6-difluorophenyl)iodine(III) trifluoromethanesulfonates
Naumann, Dieter,Gnann, Robert,Padelidakis, Vasilios,Tyrra, Wieland
, p. 79 - 82 (1995)
The reactions of bis (2,6-difluorophenyl)iodine(III) and 2,6-difluorophenylxenon(II) tetrafluoroborates with trimethylsilyl trifluoromethanesulfonate yield the corresponding bis (2,6-difluorophenyl)iodine(III) and (2,6-difluorophenyl)xenon(II) trifluoromethanesolfonates.The products were identified by NMR and vibrational spectroscopy as well as by mass spectrometry.The cation peak of an organoxenon compound has been detected for the first time by FAB mass spectrometry. - Keywords: Synthesis: (2,6-Difluorophenyl)xenon(II) trifluoromethanesulfonate; Bis(2,6-difluorophenyl)iodine(III) trifluoromethanesulfonate; NMR spectroscopy; FAB mass spectrometry
ON THE NON-EXISTENCE OF TRIMETHYLSILYL TETRAFLUOROBORATE IN ACETONE AND ACETONITRILE : THE GENERATION OF BORON TRIFLUORIDE IN WEAKLY COORDINATING SOLVENTS
Bassindale, Alan R.,Stout, Tim
, p. 1631 - 1632 (1984)
The recently proposed preparation of trimethylsilyl tetrafluoroborate actually gives trimethylfluorosilane and boron trifluoride coordinated to acetone or acetonitrile.
BEITRAEGE ZUR CHEMIE DES IODPENTAFLUORIDS TEIL II. IOD(V)-VERBINDUNGEN MIT α,ω-DIFUNKTIONELLEN ALKOHOLATEN
Frohn, Hermann Josef,Pahlmann, Wolgang
, p. 243 - 256 (1984)
Nucleophilic subsitution reactions if iodine pentaflurode with a series of homologous bifunctional alcoholates -(CH2)nO- (n=2,3,4,5,6,12), a geminal dialcoholate CCl3CH(O-)2 and a trifunctional alcoholate CH3C(CH2O-)3 protected by (CH3)3Si - groups are reported.Systems with short CH2 - chains (nX (X = SiMe3, IF4) which rearrange to mononuclear chelates IF3 of high stability.Dialcoholates with long CH2-chains (n>4) behave as bridging ligands forming stable multinuclear compounds IF4IF4 and (IF3)m (m>2). 1,4-Butanediolate is on the border line of the two systems.Products with greater subsitution IF2 (n=2,3) and IF2(OCH2)3CCH3 are also characterized.The dependence of 19F-NMR-shifts on the nature and arrangement of ligands is discussed.
Synthesis of [1-14C]-2,2-difluoroethene from [14C]-formaldehyde
Ruzicka,Qiu,Baker,Burton
, p. 59 - 65 (1994)
[1-14C]-2,2-Difluoroethene was synthesized from [14C]-formaldehyde using a modification of the Wadsworth-Emmons reaction, via formation of the intermediate (EtO)2P(O)CF214CH2OSiMe3. This highly volatile product was collected in a liquid nitrogen trap at a purity of >97% and specific activity of 0.2 mCi/mmol, with yields of 10-15%.
Direct amidation of acid fluorides using germanium amides
Hayatifar, Ardalan,Elifritz, Emily A.,Bloom, Molly B.,Pixley, Kaitlyn M.,Fennell, Christopher J.,Weinert, Charles S.
supporting information, p. 4490 - 4493 (2021/04/12)
Amide functional groups are an essential linkage that are found in peptides, proteins, and pharmaceuticals and new methods are constantly being sought for their formation. Here, a new method for their preparation is presented where germanium amides Ph3GeNR2convert acid fluorides directly to amides. These germanium amides serve to abstract the fluorine atom of the acid fluoride and transfer their amide group -NR2to the carbonyl carbon, and so function as amidation reagents.
Difluorocarbene Generation from TMSCF3: Kinetics and Mechanism of NaI-Mediated and Si-Induced Anionic Chain Reactions
García-Domínguez, Andrés,West, Thomas H.,Primozic, Johann J.,Grant, Katie M.,Johnston, Craig P.,Cumming, Grant G.,Leach, Andrew G.,Lloyd-Jones, Guy C.
supporting information, p. 14649 - 14663 (2020/10/13)
The mechanism of CF2 transfer from TMSCF3 (1), mediated by TBAT (2-12 mol %) or by NaI (5-20 mol %), has been investigated by in situ/stopped-flow 19F NMR spectroscopic analysis of the kinetics of alkene difluorocyclopropanation and competing TFE/c-C3F6/homologous perfluoroanion generation, 13C/2H KIEs, LFERs, CF2 transfer efficiency and selectivity, the effect of inhibitors, and density functional theory (DFT) calculations. The reactions evolve with profoundly different kinetics, undergoing autoinhibition (TBAT) or quasi-stochastic autoacceleration (NaI) and cogenerating perfluoroalkene side products. An overarching mechanism involving direct and indirect fluoride transfer from a CF3 anionoid to TMSCF3 (1) has been elucidated. It allows rationalization of why the NaI-mediated process is more effective for less-reactive alkenes and alkynes, why a large excess of TMSCF3 (1) is required in all cases, and why slow-addition protocols can be of benefit. Issues relating to exothermicity, toxicity, and scale-up are also noted.
