The Acetonitrile(pentafluorophenyl)xenon(II) Cation, [MeCNXe–C₆F₅]^⊕: The First Structural Characterization of a XenonCarbon Bond

Abstract

The title compound containing a xenon‐carbon bond can be prepared by fluorine‐aryl substitution in XeF2 and crystallization from acetonitrile solution. The XeC bond has been characterized for the first time by a structure analysis : it is 2.092(8) Å long. Not shown in the picture on the right is the MeCN molecule coordinated to xenon.

The First Organoxenon(IV) Compound: Pentafluorophenyldifluoroxenonium(IV) Tetrafluoroborate

“…The Cu meshes were subjected to TEM observation with an acceleration voltage of 75 kV and magnifications of 5000 ± 20 000. the increased oxidation potential of XeF 4 compared to XeF 2 , oxidatively resistant reactants and by-products with electronpoor organic groups were required. The use of B(C 6 F 5 ) 3 , which was successful in the fluoroaryl substitution of XeF 2 , [7] had to be ruled out because the nucleophilic and easily oxidizable anion [(C 6 F 5 ) 2 BF 2 ] À results from the aryl transfer. The problem of oxidizable by-products was overcome by using the recently accessible C 6 F 5 BF 2 , [8] which yields [BF 4 ] À as the by-product.…”

“…Heating an oxygen-free aqueous solution of 2'-bis(ethoxycarbonyl)propylcobalamin (2) [7] and methylcobalamin (1) [1,8] (1:2 1.6:1) at 70 8C for about 5 h (at pH 7, with protection from light) completely decomposed the organocobalamin 2. The organic decomposition products obtained after oxidation of the reaction mixture with air (in the dark and with the addition of potassium cyanide) were analyzed after extraction with deuterochloroform.…”

C6F5XeF, a versatile starting material in xenon–carbon chemistry

“…The first examples of xenon(II)-carbon compounds, salts containing the [C 6 F 5 Xe] þ cation, were prepared independently by Naumann [1] and Frohn [2] in 1989 and were structurally characterised by X-ray crystallography [3]. The development of the following decade which included alkynyl-, cycloalkenyl-, and alkenyl-in addition to arylxenon(II) compounds was summarised in two reviews [4].…”

“…Me 3 SiCN and its isotopomers Me 3 Si 13 CN and Me 3 SiC 15 N reacted spontaneously with 1 forming the asymmetric molecules C 6 F 5 XeCN (3a), C 6 F 5 Xe 13 CN (3b), and C 6 F 5 XeC 15 N (3c), respectively (Eq. (2)).…”

Pentafluorophenylxenonium ion and fluoro(pentafluorophenyl)xenon in acetonitrile: A quantum-chemical study

“…The Xe-C bonds in isolated species I and II are 2.111 and 2.099 Å, respectively, whereas in MeCN the corresponding bonds are shortened to 2.086 and 2.088 Å. The latter value is the nearest to the experimental Xe-C bond length 2.092 Å [3]. In going from the gas phase to acetonitrile solution the interatomic distance Xe · · · N in complex II increases from 2.633 do 2.661 Å and approaches the experimental value 2.681 Å found for a single crystal of [MeCN · XeC 6 F 5 ] + [(C 6 F 5 ) 2 BF 2 ] -.…”