Polysulfonylamine. XX. (1/1)‐Molekülkomplexe von Di(organosulfonyl)aminen mit Triphenylphosphinoxid. Röntgenstrukturanalyse von Dimesylamin‐Triphenylphosphinoxid (1/1)

Blaschette, Armand; Wieland, E.; Hamann, Thomas W.; Jones, Peter G.

doi:10.1002/zaac.19905890118

Cited by 6 publications

(2 citation statements)

References 22 publications

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“…The apparent contradiction between the experiment (O‐protonation of 6 and 7 ) and theory (larger PA of nitrogen atom) can be reconciled by assuming the formation of an H‐bonded complex of the type S=O···HOSO 3 H rather than the complete proton transfer. Formation of such complexes even for strong bases and acids is known in the literature, for example, Ph 3 P=O···HN(SO 2 Me) 2 …”

Section: Resultsmentioning

confidence: 99%

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

Shainyan

Chípanina

Oznobikhina

2012

J of Physical Organic Chem

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The basicity of a series of sulfonamides and carboxamides with respect to protonation and hydrogen-bonded complex formation with phenol was investigated by calculations using the Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional with the 6-311G** and 6-311++G** basis sets and by infrared spectroscopy. The effect of fluorinated substituent was studied for the two series. The proton affinity of nitrogen in sulfonamides is higher than oxygen, in contrast to carboxamides, which are protonated at oxygen. The phenyl group in benzenesulfonamide increases the basicity of both heteroatoms, but more strongly of the nitrogen, whereas in benzamide the effect on the two heteroatoms is about the same. The CF 3 group equally decreases the basicity of nitrogen and oxygen atoms in sulfonamides and carboxamides. The second fluorinated substituent decreases the basicity of oxygen in (CF 3 CO) 2 NH more strongly than of nitrogen. For sulfonamides, the same effect results in the reverse of the center of basicity from nitrogen in (MeSO 2 ) 2 NH to oxygen in (CF 3 SO 2 ) 2 NH. All studied carboxamides give H-complexes via the carbonyl oxygen, whereas for sulfonamides two types of H-complexes, with the OHÁÁÁN and OHÁÁÁO=S, were found theoretically, the latter being more stable. The exception is bisimide (CF 3 SO 2 ) 2 NH, for which only the OHÁÁÁO=S complex is stable. Experimentally, only the oxygen-bound complexes are observed. Analysis of the natural charges revealed an 'abnormal' increase of the electron density on the NH group by electron-acceptor substituents in CF 3 SO 2 NHR, which was explained using the natural bond orbital analysis by loosening of the S-N bond because of orbital interactions with the s* SÀN orbital.

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Section: Resultsmentioning

confidence: 99%

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

Shainyan

Chípanina

Oznobikhina

2012

J of Physical Organic Chem

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“…Im G egensatz zu den oben genannten Imidazol/ Im idazolid-H om okonjugaten ist es nicht notw en dig, die H ydrogen-bis(disulfonylam id)-A nionen in Tab [13], Ph3PO [14]) auf H arnstoffe als H-B rückenakzeptoren A ausdehnten. D ie d o p p elt kom plexe ionische K onstitution von 5 ist um so bem erkensw erter, als das form elanaloge A ddukt (4 -B r-C 6H 4S 0 2)2N -H -0 = C (N H M e )2 im K ri stall lediglich als einfacher N eutralm olekül-K om plex vorliegt [15].…”

Section: Darstellung Der Verbindungen Und Kurzbeschreibung Ihrer Festunclassified

Polysulfonylamine, XCVI [1]. Homokonjugate aus Di(organosulfonyl)aminen und ihren konjugierten Anionen: Vier Kristallstrukturen mit asymmetrischen [N -H ··· N ]^--Wasserstoffbrücken / Polysulfonylamines, XCVI [1]. Homoconjugates Formed from Di(organosulfonyl)amines and their Conjugate Anions: Four Crystal Structures Featuring A symmetric [ N - H ··· N ]^- Hydrogen Bonds

Wijaya

Henschel

Moers

et al. 1997

Zeitschrift Für Naturforschung B

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Polysulfonylamine, XCVI [1] Homokonjugate aus Di(organosulfonyl)aminen und ihren konjugierten Anionen: Vier Kristallstrukturen mit asymmetrischen [N -H -N ]--WasserstoffbrückenPolysulfonylam ines, X C V I [1] H om oconjugates Form ed from D i(organosulfonyl)am ines and their C onjugate A n ions: Four C rystal Structures F eatu rin g A sym m etric [ N -H -N ]-H ydrogen Bonds K arna W ijaya, D ag m ar H enschel, O liver M oers, A rm and Blaschette*, P eter G. Jones* Institut für A n organ isch e und A n alytisch e C h em ie der Technischen U niversität, Postfach 3329, D -38023 B raunsch w eig Z. N aturforsch. 52b, 1 2 1 9 -1 2 2 8 (1997); ein gegan gen am 30. Juli 1997 [ N -H --N ] " H om ocon ju gate, [ 0 -H -0 ] + H om ocon jugate, H ydrogen -bis[di(organosu lfon yl)am id e], H yd rogen -b is(l,3 -d im eth y lu rea ), Crystal Structure The follow in g com p ou n d s w ere prepared by cocrystallization o f their com p on en ts from M 0.5 M eC N (5, m onoclin ic, P 2!/n). The four structures exhibit [ ( R S 0 2)2N -H -N ( S 0 2R )2]~ anion s as rare exam ples o f interm olecular [ N -H -N ] -h o m o conjugates. The N -N distan ces o f the asym m etric hydrogen bonds are, in order, 266.9(6), 276.0(3), 291.3(4) and 279.4(2) pm , the correspon ding N -H -N angles am ounting to 137(10), 176(3), 177(4) and 177(2)°. The asym m etry o f the hydrogen bonds is clearly reflected in the geom etry o f the N S 2 groups (am ine m oieties: N -S 1 6 2 .3 -1 6 5 .2 pm, S -N -S 124 .5 -1 2 7 .1°; am ide m oieties: N -S 1 5 9 .7 -1 6 1 .8 pm , S -N -S 1 1 9 .1 -1 2 2 .6°). The dihedral angles form ed by the N S 2 plan es vary from 51.8° in 4 to 87.6° in 5. The crystal lattices o f 2 and 4 consist o f discrete ions, san dw ich-typ e [N a(12-crow n -4)2]+ com p lexes acting as the counter-ions. In 3, N a + is coord in ated in an ou t-of-cavity pattern by the five polyether oxygen atom s and further accepts tw o N a -O bonds from the am ide m oiety o f the com plex anion [N a -O (c r o w n ) 2 4 1 .5 (2 )-2 4 9 .9 (2 ), N a -O ( a n io n ) 235.0(2) and 263.9(2) pm]. The surprising structure o f 5 contains h om ocon ju gated 1,3-dim ethylurea cations [(M e N H )2C -0 -H -0 = C ( N H M e ) 2]+, which are form ed via a very strong asym m etric [ O -H -0 ] + hydrogen bond [ 0 -0 247.7(2) pm, O -H -O 172(3)°] and are associated with the am ide m o ieties o f the anions through a set o f N -H -O bon ds to form infinite chains; the M eC N m olecu les occupy lattice cavities. * Sonderdruckanforderungen an Prof. A . B laschette oder Prof. P. G. Jones.

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Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4‐fluorbenzolsulfonyl)amin‐Dimethylsulfoxid(2/1)

Blaschette

Hamann

Henschel

et al. 1993

Zeitschrift anorg allge chemie

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Aus äquimolaren Lösungen der jeweiligen Komponenten in CH2Cl2/Petrolether wurden die folgenden kristallinen Addukte erhalten: (XC6H4SO2)2NH · OS(CH3)2 mit X = H, 4CH3, 4Cl, 4Br, 4I, 4NO2 und 3NO2; [(4FC6H4SO2)2NH]2 · (OS(CH)3)2 (8); (4IC6H4SO2)2NH · OP(C6H5)3. Ein (2/1)‐Komplex aus (4‐FC6H4SO2)2NH und OP(C6H5)3 ließ sich nicht isolieren. Die Festkörperstruktur des (2/1)‐Addukts 8 wird mit der bekannten Struktur des (1/1)‐Komplexes (CH3SO2)2NH · OS(CH3)2 verglichen. Kristallographische Daten von 8 bei −95°C: monoklin, Raumgruppe C2/c, a = 2 369,9(13), b = 1 006,8(4), c = 2 772,6(13) pm, β = 110,71(4)°, U = 6,187 nm3, Z = 8. Zwei Wasserstoffbrücken NH …︁ O mit N …︁ O 275 bzw. 280 pm verknüpfen die Disulfonylamin‐Moleküle mit dem Dimethylsulfoxid‐Molekül. Das O‐Atom des letzteren ist trigonal‐planar vom S‐Atom und den zwei Brücken‐H‐Atomen umgeben.

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Polysulfonylamine. XX. (1/1)‐Molekülkomplexe von Di(organosulfonyl)aminen mit Triphenylphosphinoxid. Röntgenstrukturanalyse von Dimesylamin‐Triphenylphosphinoxid (1/1)

Cited by 6 publications

References 22 publications

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4‐fluorbenzolsulfonyl)amin‐Dimethylsulfoxid(2/1)

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