Room temperature reactions of S4N4 with (amino) diphenylphosphines, (R)Ph2P, have basically yielded two different types of SN heterocycles under two different stoichiometric conditions. Phosphiniminocyclotrithiatriazenes, (R)Ph2PNS3N3 (R = C4H8N, C5H10N, C6H12N, CH3NC4H8N, (C6H11)2 N, and (C6H5CH2)2N) have been obtained (yield 45–76%) from a 1:2 mole ratio (S4N4:(R)Ph2P) reaction, while the disubstituted S4N4 derivatives, 1,5‐[Ph2(R)PN]2S4N4 (R = C4N8N, C5H10N, and C6H12N) have been obtained (yield 30–45%) only from a 1:3.5–4 mole ratio reaction. All the 1,5‐[Ph2(R)PN]2S4N4 derivatives prepared in this study undergo a room temperature solution phase transformation to the corresponding (R)Ph2PNS3N3 heterocycles. Copyright © 1992 VCH Publishers, Inc.

Colacot J. Thomas

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Heteroatom Chemistry

The title compound (NC4H8NCH3)(C 6H5)[N(C6H11)2]P=N-S 3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) Å, 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) Å, 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) Å; 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)(C6H 5)[N(C6H11)2]P=N-S3N 3 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. © 2005 Springer Science+Business Media, Inc.

Journal of Chemical Crystallography

Crystal structure analysis of (N-methyl piperazino) (phenyl) (dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (C6H12N)Ph2P=N-S 3N3·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) Å, 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.

Crystal structure analysis of norbornadiene adduct of diphenyl hexamethylenimino phosphiniminocyclotrithiazene

The title compound (C6H5)(C4H8NO)[N(C6H 11)2]P=N-S3N3 crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) Å, b = 10.6075(1) Å, c = 14.2276(2) Å, α = 78.14(3)°, β = 79.31(1)°, γ = 65.42(2)°, V = 1319.44(6) Å3, Z = 2, and space group P1̄. The cyclotrithiazene ring adopts a "distorted chair" conformation with a deviation of 0.682(7) Å for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) Å along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety. © 2003 MAIK "Nauka/Interperiodica".

Crystallography Reports

Crystal structure analysis of (morpholino)(phenyl)(dicyclohexylamino) phosphiniminocyclotrithiazene

Room-temperature reactions of asymmetric phosphines, (Ph)(DCA)(R)P (R = Et2N-, Bu2nN-) with S4N4 in acetonitrile afforded phosphiniminocyclotrithiazenes, (Ph)(DCA)(R)P=N-S3N3 (R = Et2N-, I ; Bu2nN-, II) in modest yields (ca 50%). The heterocycles have been characterized by spectroscopic [IR, UV-vis, NMR (1H and 31P) and mass] and single crystal X-ray diffraction methods. Strikingly, the angle at P-N(4)-S(1) is 135° in I, the largest observed so far and is 119.3° in II. This is also accompanied by the shortest exocyclic S(1)-N(4) bond length of 1.537 Å observed in the case of I. In the unit cell of II, two types of molecules with slightly differing degree of deviation of the tricoordinate sulfur (0.664 and 0.673 Å from the mean plane [N(1)-S(2)-N(2)-S(3)-N(3)] are observed. Copyright © 1997 Elsevier Science Ltd.

Polyhedron

Cyclic S-N compounds and phosphorus reagents-XV [1]. Synthesis, spectral and X-ray structural characterization of (Ph)(DCA)(R)P=N-S3N3 [R=(C2H5)2N-; (n-C4H9)2N-]

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 &amp; Sons, Inc.

Reactions of S4N4 with tertiary phosphines - Synthesis of phosphiniminocyclothiazenes and their reactions

Reactions of S4N4 with diphosphines, Ph2P(X)PPh2 (X = NC4H8N, CH2CH2) have resulted in the isolation of N3S3NPPh2(X)Ph2PNS3N3 (X = NC4H8N, CH2CH2), (S)PPh2(CH2CH2)Ph2PNS3N3, and (S)PPh2NC4H8NPh2P(S) as new compounds. These heterocycles have been characterized by analytical and spectroscopic (IR, UV‐VIS, 1H and 31P‐NMR, and MS) techniques. Copyright © 1993 Verlag GmbH &amp; Co. KGaA, Weinheim

ZAAC ‐ Journal of Inorganic and General Chemistry

Reactions of S4N4 with diphosphines, Ph2P(X)PPh2 (X = NC4H8N, CH2CH2)

(Morpholino)diphenylphosphine, unlike PPh3, gives only two new compounds, (OC4H8N)Ph2PNS3N3, (1), and 1,5-[(OC4H8N)Ph2PN]2S 4N4, (2), on reacting with S4N4. The reaction temperature, solvent, and mole ratio of the reactants are critically important in their synthesis. For the first a ring contraction of compound (2) to compound (1) in solution at room temperature has been observed and evidence for the elimination of the 'NSR' group (R = phosphinimino group) obtained.

Journal of the Chemical Society, Dalton Transactions

Cyclic sulphur-nitrogen compounds and phosphorus reagents. Part 2. Reactions of tetrasulphur tetranitride with (morpholino)diphenylphosphine. First observation of the ring contraction of 1,5-[(OC4H8N)Ph2PN]2S 4N4 to (OC4H8N)Ph2PNS3N3 in solution

Journal	Heteroatom Chemistry
ISSN	10427163
Open Access	No