In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 630, No. 8-9 ( 2004-08), p. 1235-1244
Abstract:
About the Formation of Trithiatetrazocine Derivatives from Bicyclic Carbon‐Sulfur‐Nitrogen Heterocycles, RCN 5 S 3 With AsF 5 F 3 CCN 5 S 3 ( 1a ) forms a 1:1 adduct F 3 CCN 5 S 3 ˙ AsF 5 ( 2 ), which slowly decomposes in CDCl 3 solution to give [F 3 CCN 4 S 3 ] + [AsF 6 ] — ( 3 ) a salt with an cationic eight membered heterocycle. AsF 5 attacks the bridging nitrogen atom, the nitrogen carrying the highest negative charge. By contrast, in the protonated compound [F 3 CCN 5 S 3 H] + [AsF 6 ] — ( 6 ) one of the nitrogen atoms adjacent to the ring‐carbon atom is attacked, which can be explained by different basicities of the nitrogen atoms. PPh 3 and AsPh 3 open the bicycles RCN 5 S 3 ( 1 ) forming phosphanimino‐ and arsaniminotetrazocine derivatives RCN 4 S 3 N=EPh 3 (R = F 3 C, E = P (endo), 4a ; E = As (endo), 5a ; R = Me 2 N, E = P (endo), 4c ), respectively. The mechanism proposed for this reaction in the literature, is confirmed by the preparation of [TAS] + [F 3 CCN 5 S 3 NC(NH 2 )CF 3 ] — ( 7 ). The structures of 2 , 3 , 4a , 4c , 5a , 6 and 7 , determined by X‐ray diffraction, will be discussed.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v630:8/9
DOI:
10.1002/zaac.200400080
Language:
English
Publisher:
Wiley
Publication Date:
2004
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
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