Preparation and structural characterization of 1-phenyl-1-(dicyclohexylamino)cyclo-1-phospha-3,5-dithia-2,4,6-triazene - a phosphathiazene with different substituents on phosphorus
01 Feb 1992-Phosphorus Sulfur and Silicon and The Related Elements (GORDON BREACH SCI PUBL LTD)-Vol. 65, pp 257-259
TL;DR: In this article, the reaction of S4N4 with dicyclohexylaminophenyl-(2-aminopyridyl)phosphine in MeCN at room temperature leads to the formation of the novel compound Ph(cycloHex2 N)PS2 N3.
Abstract: The reaction of S4N4 with dicyclohexylaminophenyl-(2-aminopyridyl)phosphine in MeCN at room temperature leads to the formation of the novel compound Ph(cycloHex2 N)PS2 N3. An X-Ray structure determination confirms that this, compound consists of a six-membered PSN-ring with two different substituents at phosphorus.
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TL;DR: The chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry as mentioned in this paper.
Abstract: In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)–nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar PN bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day-by-day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce new types of heterocycles. In this paper, the chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry. Copyright © 2009 John Wiley & Sons, Ltd.
79 citations
TL;DR: The reaction of S4N4 with phosphines of the type PhPR2 (1,5) and PhR′PR [6−11 (R′ = dicyclohexylamino), R: 1,6 = pyrrolidino, 2,7 = piperidino; 3,8 = morpholino; 4,9 = N-methylpiperazino; 5,10 = hexamethylenimino; and 11 = anilino] afford the phosphiniminocyclotrithiazene
Abstract: The reactions of S4N4 with phosphines of the type PhPR2 (1–5) and PhR′PR [6–11 (R′ = dicyclohexylamino), R: 1,6 = pyrrolidino; 2,7 = piperidino; 3,8 = morpholino; 4,9 = N-methylpiperazino; 5,10 = hexamethylenimino; and 11 = anilino] afford the phosphiniminocyclotrithiazene derivatives, 12–22 at room temperature. Only in the case of the phosphine 10 was the disubstituted derivative 23 isolated (in 65% yield). The trithiazene derivatives of the chiral phosphines in refluxing CH3CN produce the acyclic compounds PN–S3N, 24–27 in ca. 60% yield. Norbornadiene reacts at room temperature with the cyclotrithiazene derivatives to give the addition products 28–35. P=N–S3N3 derivatives are found to be stable in 2M NaOH. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 225–232, 1997.
10 citations
TL;DR: In this article, the stability aspects from the mass spectral fragmentation patterns of two phosphiniminocyclotrithiazenes of the type (C6H5)[(C 6H11)2N](R2N)P˭N−S3N3 [R‒Me (1) and n-Bu (2)].
Abstract: GRAPHICAL ABSTRACT Abstract This study has been directed toward understanding the stability aspects from the mass spectral fragmentation patterns of two phosphiniminocyclotrithiazenes of the type (C6H5)[(C6H11)2N](R2N)P˭N−S3N3 [R‒Me (1) and n-Bu (2)]. Most of the structural features of the two ring systems considered are comparable for both the heterocycles. Some of the fragments that are formed under the operated mass spectral conditions are SN, S2N2, S3N, S3N2, S3N3, and S3N4, among others. Most of these observed fragments are already known to exist either as stable entities or as oligomerized species, and they are found to possess various applications.
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TL;DR: In this article, the X-ray structure analysis of 3a (Rf CF3) is reported, which contains an eight-membered ring with 1,3-P(CF3)2 groups.
Abstract: Aus den (Disilylamino)phosphanen (Rf)2P – N(SiMe3)2 (Rf CF3, C2F5) und S3N2Cl2 werden unter Abspaltung von Me3SiCl und S8 neue Cyclophosphadithiatriazene der Zusammensetzung (Rf)2PN3S2 (1a, b) erhalten. Als Nebenprodukte treten Phosphanimide (Rf)2P(Cl) NSiMe3 (2a, b) auf. 1a, b bilden mit Norbornadien 1:1-Addukte 3a, b. Die Rontgenstrukturanalyse von 3a (Rf CF3) wird mitgeteilt. Aus 1a bildet sich nach mehrtagigem Stehenlassen eine kristalline Verbindung [(CF3)2PN2S]2 (4), deren Rontgenstrukturbestimmung einen achtgliedrigen Ring mit 1,3-P(CF3)2-Gruppen zeigt.
(Disilylamino)phosphanes (Rf)2P – N(SiMe3)2 – Precursors for PN3S2 Rings
The reactions of the (disilylamino)phosphanes (Rf)2P – N(SiMe3)2 (Rf CF3, C2F5) with S3N2Cl2 lead to new cyclophosphadithiatriazenes of composition (Rf)2PN3S2 (1a, b) with elimination of Me3SiCl and S8. By-products are (Rf)2P(Cl) NSiMe3 (2a, b). Reaction of 1a, b with norbornadiene yields 1:1 adducts 3a, b. The X-ray structure analysis of 3a (Rf CF3) is reported. When 1a is allowed to stand for several days a crystalline compound of composition [(CF3)2PN2S]2 (4) is formed. The X-ray structure analysis shows that 4 contains an eight-membered ring with 1,3-P(CF3)2 groups.
14 citations
TL;DR: In this article, the authors used 31P nmr spectroscopy to obtain an activation energy of 102.4 ± 6.0kJm−1 for the release of the NSN fragment from Me2PS3N5.
Abstract: The oxidative addition of Cl2 (using SO2Cl2) to the six-membered ring (R2PN)(SN)2 (R = Me, Ph) produces the mixed phosphazene–thiazyl heterocycles, (R2PN)(NSCl)2, which react with Me3SiNSNSiMe3 to give the bicyclic compounds R2PS3N5. The latter undergo thermal decomposition, at ca. 100 °C in toluene, via reductive elimination of an NSN unit to regenerate (R2PN)(SN)2 in high yield. Kinetic measurements of this process, using 31P nmr spectroscopy, yield an activation energy of 102.4 ± 6.0 kJ mol−1 for the release of the NSN fragment from Me2PS3N5. The thermolysis route has been used to prepare the thermally unstable (F2PN)(SN)2, characterized as a 1:1 adduct with norbornadiene.
11 citations