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Journal ArticleDOI

Crystal structure analysis of norbornadiene adduct of diphenyl hexamethylenimino phosphiniminocyclotrithiazene

01 Jan 2004-Journal of Chemical Crystallography (Kluwer Academic Publishers-Plenum Publishers)-Vol. 34, Iss: 1, pp 19-23

AbstractThe title compound (C6H12N)Ph2P-N $$---$$ S3N3 ⋅ C7H8 crystallizes in the monoclinic space group P21/n with unit cell dimensions: a = 9.9200(5), b = 16.3316(11), c = 15.7009(17) A, β = 91.99(1)°, and Z = 4. The cyclotrithiazene ring adopts a chair conformation with equal bond distances and the norbornadiene is fused in an exo, exo fashion to the heterocycle. Norbornadiene addition to the cyclotrithiazene influences the bonding pattern in the ring as well as the P $$---$$ N $$---$$ S moiety.

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Citations
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Journal ArticleDOI
Abstract: The title compound (NC4H8NCH3)(C6H5)[N(C6H11)2]P{—N–S3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) A, α = 71.75(1)∘, β = 80.65(2)∘, γ = 65.93(1)∘, and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) A, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P{—N4–S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) A; but the bond angle is large 135.3(4)∘. The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents (R) in the (R)(C6H5)[N(C6H11)2]P{—N–S3N3 series. On the other hand, the S1–N4 bond distances are negatively correlated (R = −0.94) with the P{—N4–S1 bond angle in the above series.

4 citations

Journal ArticleDOI
Abstract: Iodination reactions of various phosphiniminocyclotrithiazenes [R3PNS3N3; R = (i) phenyl-, (ii) morpholino-, and (iii) p-chlorophenyl-] have been studied under different experimental conditions. Iodination of Ph3PNS3N3 yields interesting products such as [(Ph3PN)2S3N3]I3, ((Ph3PN)3S)2I4, (Ph3PNH2)I3, ((Ph3PSI2)2I2, and [(Ph3PN)3SO]2I6 depending on the experimental conditions. All the products have been isolated and characterized by the spectroscopic and analytical techniques.

2 citations


References
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Journal ArticleDOI
Abstract: Ausgehend von FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) und Fe(C5H4AsCl2)2 (4) werden drei-, vier-, funf- und achtgliedrige Heterocyclen mit Ferrocenyl-Substitutenten synthetisiert (Fc = Ferrocenyl). Durch Umsetzung von 1 mit 2 in Gegenwart von DBU entsteht (FcP)n, das mit (Ph3P)2Pt(C2H4) zu (7) reagiert. Der analoge As2Pt-Ring 9 ist uber (FcAs)3 (8) in guter Ausbeute zuganglich. Die Reduktion von 1 mit LiAlH4 liefert (FcP)4 (10). Ein funfgliedriger Arsen-Schwefel-Heterocyclus, Fc2As2S3 (12), entsteht durch Umsetzung von FcAs=P(2,4,6-tBu3C6H2) (11) mit Schwefel. FcAsCl2 (3) reagiert mit Me3SiNSNSiMe3 zu FcAs(NSN)2AsFc (13), das einen achtgliedrigen As2S2N4-Ring enthalt. Dessen Komplexierung mit (Norbornadien)M(CO)4 fuhrt zu den Tetracarbonyl-Komplexen [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). Ein Arsenuberbrucktes Ferrocenophan 16 kann bei der Reaktion von Fe(C5H4Li)2 × TMEDA mit AsCl3 isoliert werden. Auch die Umsetzung von 4 mit Me3SiNSNSiMe3 liefert ein kondensiertes Ferrocenophan-Derivat der Zusammensetzung (C5H4)2FeAs2N6S4 (17). Die Molekulstrukturen von 13 und 17 wurden rontgenographisch bestimmt. Inorganic Ring System Containing Ferrocenyl Substituents Three-, four-, five-, and eight-membered heterocycles are synthesized starting from FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) and Fe(C5H4AsCl2)2 (4) (Fc = Ferrocenyl). Treatment of 1 with 2 in the presence of DBU yields (FcP)n, which reacts with (Ph3P)2Pt(C2H4) to give (7). The corresponding As2Pt ring system 9 is available in high yield via (FcAs)3 (8). The reduction of 1 with LiAlH4 yields (FcP)4 (10). A five-membered arsenic sulfur heterocycle, Fc2As2S3 (12), is formed in the reaction of FcAs=P(2,4,6-tBu3C6H2) (11) with sulfur. FcAsCl2 (3) reacts with Me3SiNSNSiMe3 to give FcAs(NSN)2AsFc (13), which contains an eight-membered As2S2N4 ring. Its complexation with (norbornadiene)M(CO)4 leads to the tetracarbonyl complexes [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). An arsenic-bridged ferrocenophane 16 can be isolated from the reaction of Fe(C5H4Li)2 x TMEDA with AsCl3. The reaction of 4 with Me3SiNSNSiMe3 also produces a condensed ferrocenophane derivative, (C5H4)2FeAs2N6S4 (17). The molecular structures of 13 and 17 have been determined by X-ray diffraction.

55 citations

Journal ArticleDOI
Abstract: The reaction of norbornadiene with (triphenylphosphoranediyl)aminocyclotrithiatriazene produces the cycloadduct Ph3PN—S3N3•C7H8. The crystal and molecular structure of this compound has been determ...

26 citations