Polysulfonylamine. LXXII [1]. Triphenylcarbenium‐ und Triphenylphosphonium‐di(fluorsulfonyl)amid: Zwei Kristallstrukturen mit geordneten (FSO₂)₂N^⊖‐Lagen

Abstract

Reaktion von HN(SO2F)2 in CH2Cl2 mit Ph3P, Ph3PO oder Collidin (=B) ergibt die Verbindungen Ph3PH⊕[(FSO2)2N]⊖ (3), Ph3PO · HN(SO2F)2 und BH⊕ [(FSO2)2 · N]⊖ (7). Das durch Metathese von Ph3CBr mit [(C6H6)AgN · (SO2F)2] in CH2Cl2 erhältliche Carbeniumsalz Ph3C⊕ [(FSO2)2N]⊖ (5) kristallisiert aus Chloroform/Petrolether als Monosolvat Ph3C⊕ [(FSO2)2N]⊖ · CHCl3 (6). In Kombination mit einer sterisch gehinderten Base, z. B. Collidin, eignet sich 5 als Reagens für die Tritylierung schwach CH‐acider Moleküle (Beispiele: MeCN → Ph3CCH2CN, Aceton → Tritylaceton; Koppelprodukt: 7). Die Kristallstrukturen der ionischen Festkörper 3 (monoklin, Raumgruppe P21/n) und 6 (monoklin, P21/c) wurden durch Röntgenbeugung bei −130°C ermittelt; die häufig zu beobachtende kristallographische Unordnung der (FSO2)2N‐Gruppe trat nicht auf. Wie in der bekannten Struktur des Tetraphenylarsonium‐Salzes besitzt das Anion in 3 und 6 eine gestaffelte Konformation mit annähernder C2‐Symmetrie (Gesamtmittelwerte: SNS 121,4°, NS 156,2, SO 141,6, SF 156,6 pm). In 6 ist das CHCl3‐Molekül über eine Dreizentren‐Wasserstoffbrücke des Typs CH(…︁O)2 mit zwei Sauerstoffatomen des Anions zu einem sechsgliedrigen Ring verknüpft [R 12(6)‐Muster; H …︁ O 234 und 262 pm]. Die Anionen und Kationen von 3 sind durch eine Dreizentren‐Brücke des Typs PH(…︁O)2 zu Ketten assoziiert [C 12(6)‐Muster; H …︁ O 237 und 254 pm]. Das Ph3C⊕‐Kation in 6 besitzt eine Propeller‐Form mit drei koplanaren zentralen Bindungen (CC‐Mittelwert: 144,5 pm); die Interplanarwinkel zwischen den Phenylringen betragen 52,7, 56,4 und 60,1°.

Synthesis of Poly- and the First Perfluoroalkyl-N(SO2F)2Derivatives: Improved Methods for the Preparation of XN(SO2F)2(X = H, Cl) and Single-Crystal Diffraction Studies of HN(SO2Cl)2, HN(SO2F)2, and CF3CH2N(SO2F)2

“…In covalent R−N(SO 2 F) 2 derivatives, the S−O bond distances lie in the range 1.375−1.405 Å, which is close to the S−O bond length found in SO 2 F 2 (1.405 Å), where the S−O bond order is assigned as 2.0 by Gillespie et al These S−O distances are, however, shorter than the corresponding bond lengths found in CsN(SO 2 F) 2 [1.421(3) Å], , (C 6 H 5 ) 3 XN(SO 2 F) 2 [X = C, 1.414(3) Å; X = P, 1.419(2) Å], Me 3 PbN(SO 2 F) 2 [1.418(6) Å], NH 2 (SO 3 ) - (1.457 Å), , NH(SO 3 ) 2 2- [1.449 Å], , and N(SO 3 ) 3 3- (1.468 Å) . An increase in S−O bond order is observed in going from an ionic to a covalently bonded R−N(SO 2 F) 2 derivative.…”

“…Although HN(SO 2 Cl) 2 and its derivatives have been known for over 3 decades, no structures with the N(SO 2 Cl) 2 moiety have been reported . There has been a recent increase in interest in the structures of compounds containing the N(SO 2 X) 2 moiety. ,,,, The modifications we have made to the synthetic procedure for the preparation of HN(SO 2 F) 2 afford this acid, as well as its fluorinated analogue in high purity. The availability of diffraction quality crystals formed at low temperatures for these acids and CF 3 CH 2 N(SO 2 F) 2 provided an opportunity to study the cryogenic crystal and molecular structures of these compounds.…”

“…More recent reports deal with some new N(SO 2 F) 2 derivatives, such as R 3 EN(SO 2 F) 2 (E = Si, , Ge, Sn, , Pb 3 ; R = alkyl), [Ph 3 C][N(SO 2 F) 2 ], [Ph 3 PH][N(SO 2 F) 2 ], and their crystal structures. The crystal structure of CsN(SO 2 F) 2 was determined independently by two groups. , Also syntheses of an azido derivative, N 3 N(SO 2 F) 2 , and the crystal structure of S[N(SO 2 F) 2 ] 2 were reported.…”

Triphenylphosphonium perchlorate

“…In the perchlorate anion O-Cl-O angles lie in the range 106.03 (18)-113.0 (4) . The P-H distance of 1.25 (5) Å in (I) is comparable to that in [Ph 3 PH] 2 [SnCl 6 ] [1.285 (3) Å ; Yatsenko et al, 1986], Hiemisch et al, 1996], but shorter than that in [Ph 3 PH]Br [1.61 (9) Å ] where the proton is directed towards the bromide anion (Bricklebank et al, 1993). The molecular structure of (I), showing the atom-numbering scheme, and with displacement ellipsoids at the 50% probability level for non-H atoms.…”

Polysulfonylamines. CXXI. ThreeN,N-disulfonylated 1-adamantylamines

“…Tabulation of all data available at this time suggests that the degree of N---C bond lengthening in N-alkyl disulfonylamines correlates with the stability order of the carbocations derived from the N-alkyl groups. Corroborative evidence is seen in the related trityl compound Ph3C+-N(SO2F)2, which is purely ionic in the solid state (Hiemisch et al, 1996). N-Organyl disulfonylamines, including (I)-(III), generally display a nearly planar central grouping formed by the N, C and two S atoms bonded to it.…”