Xenon-nitrogen bonds. The synthesis and characterization of [imidobis(sulfuryl fluoride)]xenon(II) derivatives Xe[N(SO2F)2]2, FXeN(SO2F)2 and [(FSO2)2NXe]2F+AsF6- and the radical .cntdot.N(SO2F)2

Abstract

Zwei neue Xe(II)‐Derivate (III) und (IV), in denen Xe an das N‐Atom eines elektronegativen Liganden gebunden ist, werden durch Umsetzung von XeF2 mit HN(SO2F)2 bei niedrigeren Temp. erhalten.

Nature of the XeVI−N Bonds in F6XeNCCH3and F6Xe(NCCH3)2and the Stereochemical Activity of Their Xenon Valence Electron Lone Pairs

“…ÀNb onds occur for trigonal planar (sp 2 -hybridized) inorganic nitrogen ligandsd erived from the (FO 2 S) 2 N( imidobis(sulfurylfluoride)) group, that include FXeN(SO 2 F) 2 , [15][16][17] + , [19] the related (CF 3 O 2 S) 2 N( imidobis(sulfuryltrifluoromethyl)) group, which is solely represented by (Xe[N-(SO 2 CF 3 ) 2 ] 2 ), [20] and the sulfur-nitrogen-fluorine cations derived from NSF 3 ,n amely, [ F 4 S=NXe] + [21] and [F 4 S=NXe···NSF 3 ] + . [22] The only examples in which xenon is bonded to sp 3 -hybridized nitrogen are [F 5 Te N(H)Xe]…”

Xenon–Nitrogen Chemistry: Gas‐Phase Generation and Theoretical Investigation of the Xenon–Difluoronitrenium Ion F2NXe+

“…Theoretical calculations are also extensively employed to aid the interpretation of the experiments, and to explore the conceivable existence of still uncovered molecules and ions. [8,[14][15][16][17] The first xenon-nitrogen species, FXeNA C H T U N G T R E N N U N G (SO 2 F) 2 , was observed in 1974 by spectroscopic methods, [18] and the related compounds Xe[NA C H T U N G T R E N N U N G (SO 2 [19,20] and Xe[NA C H T U N G T R E N N U N G (SO 2 CF 3 ) 2 ] 2 [21] were subsequently reported. It was, however, only in 1982 that an X-ray crystallographic study of FXeNA C H T U N G T R E N N U N G (SO 2 F) 2 furnished the first definitive proof for the existence of a Xe À N bond.…”

“…[22,23] In subsequent years, xenonnitrogen chemistry was considerably expanded, noticeably by Schrobilgen and co-workers, [24][25][26][27][28][29][30][31][32][33] and evidence for novel compounds is still emerging. [34,35] In general, apart from the molecular species FXeNA C H T U N G T R E N N U N G (SO 2 F) 2 , [18,20,22,23] Xe[N-A C H T U N G T R E N N U N G (SO 2 F) 2 ] 2 , [20,24] and Xe[NA C H T U N G T R E N N U N G (SO 2 CF 3 ) 2 ] 2 , [21] the xenon-nitrogen compounds observed in the condensed phase are salts of Xe À N cations and counteranions such as AsF 6 À , Sb 3 F 16 À , and BY 4 À (Y=CF 3 , C 6 F 5 ). The Xe À N cations can be in turn divided into two groups.…”

“…In the present study, by using a procedure strictly analogous to that employed to generate the gaseous F 3 SiÀXe + [37] and F 3 GeÀXe + , [38] we could form in the gas phase the xenon-difluoronitrenium cation F 2 NÀXe + . This species is still unreported, but it is of interest to note that the N 2 F 4 and Xe products observed so far from the reaction between XeF 2 and HNF 2 were ascribed to the formation of F 2 NXeF, [20] even though neither this intermediate nor other related ionic species could be detected even at lower temperatures. According to our theoretical calculations, F 2 NÀ Xe + is indeed a weak electrostatic complex between NF 2 + and Xe, intrinsically less stable than the other xenon-nitrenium ions observed in the condensed phase.…”

Neutral rare-gas containing charge-transfer molecules in solid matrices. III. HXeCN, HXeNC, and HKrCN in Kr and Xe

“…The first xenon-nitrogen bond in FXeN͑SO 2 F͒ 2 was reported in 1974 by DesMarteau and LeBlond and up to date this and a few similar compounds seem to be the only examples of Xe-N bonding. [3][4][5][6] In 1979, Turbini et al 7 reported the synthesis of Xe͑CF 3 ͒ 2 with a xenon-carbon bond but its unequivocal spectroscopic characterization is still lacking. During the last few years, a number of compounds with Xe-C bonds have been synthesized and characterized, including ionic compounds (C 6 F 5 Xe) ϩ (C 6 F 5 BF 3 )…”