420-56-4Relevant articles and documents
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.
C-F Bond Activation of P(C6F5)3 by Ruthenium Dihydride Complexes: Isolation and Reactivity of the missing Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF
Cybulski, Mateusz K.,Davies, Caroline J. E.,Lowe, John P.,Mahon, Mary F.,Whittlesey, Michael K.
, p. 13749 - 13760 (2018)
The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is the five-coordinate complex Ru(IMe4)2(PF2{C6F5})(C6F5)H (2), which is formed via a complex series of C-F/P-C bond cleavage and P-F bond formation steps. In contrast, hydrodefluorination of all six ortho C-F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF (3). NaBArF4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. The treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv) afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3, respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).
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
A Convenient Synthesis of Trimethylsilyl Fluoride
Della, Ernest W.,Tsanaktsidis, John
, p. 407 (1988)
Trimethylsilyl fluoride 1 is conveniently prepared by the reaction of trimethylsilyl trifluoromethanesulfonate with potassium fluoride in dimethylformamide containing 18-crown-6 ether.
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.
Infrared Laser Photodetachment of Electrons from Vibrationally Excited Allyl Anions
Wight, Charles A.,Beauchamp, J. L.
, p. 4426 - 4430 (1984)
Infrared laser photodetachment of allyl anions has been investigated using the techniques of ion cyclotron resonance (ICR) spectroscopy.Facile detachment of vibrationally excited anions occurs with a phenomenologically defined cross section, ?* = (6.5 +/- 2) x 1E-20 cm2 at 945 cm-1, using a low-power CW CO2 laser.The detachment yield decreases with increasing photon energy in the range 900-1100 cm-1.Photodetachment from vibrationally relaxed anions also occurs but whit a much lower cross section, ? = (6.3 +/- 3) x 1E-23 cm2.When fluoride ion reacts with allyltrimethylsilane, about 30percent of the nascent allyl anions are vibrationally excited.The predominant relaxation mechanism below 1E-6 torr is radiative emission with a measured rate constant of 53 +/- 10 s-1.
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.
(CF3)2Cd*D UND (CF3)2Zn*D: NEUE REAGENZIEN FUER DIFLUORCARBEN-REAKTIONEN
Lange, Horst,Naumann, Dieter
, p. 299 - 308 (1985)
During the thermal decomposition of (CF3)2Cd and (CF3)2Zn complexes primarily difluorocarbene is eliminated.The formation of CF2 is unambiguously proved by matrix i.r. spectroscopy.Both (CF3)2Cd*D and (CF3)2Zn*D are excellent CF2 sources, which can easily be prepared and handled, and which undergo CF2 reactions even at low temperature.CF2 insertion was found during the reaction of (CF3)2Te with (CH3)2Cd via the intermediate formation of a CF3Cd compound to form CH3TeCF2CH3. (CF3)2Cd*glyme reacts with (CH3)3Si(OCOCF3) to CF3Cd(OCOCF3)*glyme; during this reaction CF2 is also eliminated.
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%.
