118798-75-7Relevant academic research and scientific papers
Xenon(IV)-carbon bond of [C6F5XeF2]+; Structural characterization and bonding of [C6F5XeF2][BF4], [C6F5XeF2][BF4]·2HF, and [C6F5XeF2][BF4]· n NCCH 3 (n = 1, 2); And the fluorinating properties of [C6F5XeF2][BF4]
Koppe, Karsten,Haner, Jamie,Mercier, Hlne P. A.,Frohn, Hermann-J.,Schrobilgen, Gary J.
, p. 11640 - 11661 (2015/01/16)
The [C6F5XeF2]+ cation is the only example of a XeIV-C bond, which had only been previously characterized as its [BF4]- salt in solution by multi-NMR spectroscopy. The [BF4]- salt and its new CH3CN and HF solvates, [C6F5XeF2][BF4]·1.5CH3CN and [C6F5XeF2][BF4]·2HF, have now been synthesized and fully characterized in the solid state by lowerature, single-crystal X-ray diffraction and Raman spectroscopy. Crystalline [C6F5XeF2][BF4] and [C6F5XeF2][BF4]·1.5CH3CN were obtained from CH3CN/CH2Cl2 solvent mixtures, and [C6F5XeF2][BF4]·2HF was obtained from anhydrous HF (aHF), where [C6F5XeF2][BF4]·1.5CH3CN is comprised of an equimolar mixture of [C6F5XeF2][BF4]·CH3CN and [C6F5XeF2][BF4]·2CH3CN. The crystal structures show that the [C6F5XeF2]+ cation has two short contacts with the F atoms of [BF4]- or with the F or N atoms of the solvent molecules, HF and CH3CN. The lowerature solid-state Raman spectra of [C6F5XeF2][BF4] and C6F5IF2 were assigned with the aid of quantum-chemical calculations. The bonding in [C6F5XeF2]+, C6F5IF2, [C6F5XeF2][BF4], [C6F5XeF2][BF4]·CH3CN, [C6F5XeF2][BF4]·2CH3CN, and [C6F5XeF2][BF4]·2HF was assessed with the aid of natural bond orbital analyses and molecular orbital calculations. The 129Xe, 19F, and 11B NMR spectra of [C6F5XeF2][BF4] in aHF are reported and compared with the 19F NMR spectrum of C6F5IF2, and all previously unreported J(129Xe-19F) and J(19F-19F) couplings were determined. The long-term solution stabilities of [C6F5XeF2][BF4] were investigated by 19F NMR spectroscopy and the oxidative fluorinating properties of [C6F5XeF2][BF4] were demonstrated by studies of its reactivity with K[C6F5BF3], Pn(C6F5)3 (Pn = P, As, or Bi), and C6F5X (X = Br or I).
[(C6F5)2if2][BF4], the first salt with the electrophilic cation [(C6F5) 2if2]+: Synthesis, reactivity, and structure
Frohn, Hermann-Josef,Wenda, Andre,Floerke, Ulrich
, p. 764 - 770 (2009/04/13)
The substitution of hypervalently bonded fluorine atoms in C 6F5IF4 was performed with C6F 5BF2 and resulted in the new salt [(C6F 5)2IF2][BF4]. The iodonium(V) salt was characterized by multi-NMR and Raman spectroscopy and X-ray crystal structure analysis. The fluorinating ability of the new electrophilic cation [(C6F5)2IF2]+ was exemplified in reactions with monovalent iodine compounds (C6F 5I, p-FC6H4I, and I2) and with electron-poor tri(organyl)pnictanes ER3 (E = P, As, Sb, Bi; R = C6F5). In a heterogeneous reaction with CsF in MeCN the [(C6F5)2IF2]+ cation forms the dinuclear [{(C6F5)2IF 2}2F]+ cation.
Structures of Pentaarylbismuth Compounds
Schmuck, Arno,Leopold, Dieter,Wallenhauer, Stephan,Seppelt, Konrad
, p. 761 - 766 (2007/10/02)
Rose-colored, dichroitic pentakis(4-methylphenyl)bismuth has an intermediate structure between trigonal bipyramidal and square-pyramidal.It cocrystallizes with (LiCl*2 THF)2.The LiCl forms an almost regular rectangle with two short (195 pm) and two long (235 pm) bonds.Red Bi(4-CH3C6H4)3(2,6-F2C6H3)2 is very similar to square pyramidal Bi(C6H5)3(2,6-F2C6H3)2: The structural isomerism of yellow Bi(4-CH3C6H4)3(2-FC6H4)2 (trigonal bipyramidal) and violet Bi(C6H5)3(2-FC6H4)2 (square pyramidal) is not found here.Orange red, dichroitic Bi(C6H5)3(C12H8) remains in adistored square pyramidal structure in spite of the constraints of the 2,2'-biphenylylene ring system.The square pyramidale geometry seems to dominate in bismuth chemistry of this type, in contrast to P, As, and Sb.However, the structure of (C6F5)3BiF2 shows an almost regular trigonal bipyramid, as expected.The latter cocrystallizes as (C6F5)3BiF2*2 Bi(C6F5)3, so the structure of Bi(C6F5)3 is elucidated also.
On pentavalent perfluoroorgano bismuth compounds
Tyrra, W.,Naumann, D.
, p. 1949 - 1951 (2007/10/02)
The reactions of Bi(Rf)3 (R = CF3, C6F5) with a series of oxidizing halogenation reagents have been investigated.From the reactions of Bi(Rf)3 with Cl2, Br2, I2, ICl, and IF5 no oxidation to Bi(V) compounds can be detected; in all cases the Bi(III) halides and the corresponding RfX compounds are formed.Only the reaction of Bi(C6F5)3 with XeF2 yields the perfluoroorgano bismuth(V) compound Bi(C6F5)3F2.Key words: bismuth perfluoroorganic compounds, polar perfluoroorganylations, oxidation with xenon difluoride.
Structures of Pentaarylbismuth Compounds
Schmuck, Arno,Seppelt, Konrad
, p. 803 - 808 (2007/10/02)
Pentaarylbismuth compounds were synthesized by the known reaction Ar3BiX2 + 2 Ar'Li ---> 2 LiX + BiAr3Ar'2.Whenever possible they were characterized by single-crystal X-ray structure determination.In two cases almost ideal square-pyramidal geometry was found, in a third case there were two different molecules in the unit cell, both again with square-pyramidal geometry.None of these novel bismuth pentaaryls exhibit the deep coloration and the dichroism of Bi(C6H5)5. - Key Words: Bismuth organic compounds / Fluorinated aromatic rings / Square pyramidal bismuth
