Attempted 1,3‐trimethylsilyl migration in Me₃SiPSNR system

Abstract

A dimer of thioxo-N-t-butylimino(trimethy1siloxy)-phosphorane 5 has been prepared by reaction of tris(trimethylsily1)phosphine with N-sulfiny1-Ntert-butylamine. The structure of 5 has been confirmed by X-ray analysis data. l-Aza-2-thia-3-phosphaallene 1, thiaphosphaziridine 3, iminophosphine P-sulfide 4 are postulated as intermediates of the reaction studied.

Syntheses and characterization of functionalized cyclodiphosphazane-based frameworks

“…In addition, the solid isolated was not qualitatively pure to be conclusive of the successful formation, despite the observation of distinct peaks (i.e. two sets of doublets in the aromatic region (δ 7.65 -7.34 ppm) and singlet signals at δ 1.74 ppm) on the 1 S1 1.9097(14), P1-O3 1.610(2), P2-O1 1.676(2), P1-N1 1.666(3), P1-N2 1.658(3), P2-N1 1.717(2), P2-N2 1.711(3); Selected bond angles (°): N1-P1-N2 84.58(12), N1-P2-N2 81.47(12), P1-N1-P2 96.22(12), P1-N2-P2 96.70(13), N1-P1-O3 109.83(12), N2-P1-O3 110.70(13), O1-P2-N1 103.70(12), S1-P1-O3 106.73(9), P1-O3-C13 126.07(18).…”

“…As most of the examples are relevant and pertain to main group chemistry, which is the focus of this thesis, they will illustrate the concept and benefits of mechanochemistry. 1). They then also demonstrated that the latter compound can be readily synthesized via mechanochemical milling of rhenium(I) hexacarbonyl, TEAB and oxone in a "one-step multi-component" manner.…”

“…cyclotetraphosphazanes. [1][2][3][4][5][6][7][8] Figure 1.1. Examples of phosph(III)azane-based frameworks ranging from acyclic, fused rings, cyclic, cages to anionic derivatives.…”

“…Examples of monochlorocyclodiphosph(III)azanes. [53][54][55] Another class of commonly used chlorocyclodiphosph(III)azanes is the monochloro derivatives, [ClP(μ-NR)2P(NR 1 R 2 )] (R = R 1 but not R 2 or, R ≠ R 1 and R 2 , R 1 = R 2 ). Some examples of monochlorocyclodiphosph(III)azanes are shown in Fig.…”

“…The resulting filtrate was concentrated to yield white pure solid. Yield: 0.091 g (15 %);1 H NMR (CDCl3, 400 MHz): δ 2.53 (d, 2 JP-H = 7.2 Hz, 2H, N-H), 2.03 (s, 6H, CH), 1.84 (s, 12H, C(CH2)3), 1.63 (t, 3 JH-H = 2.8 Hz, 12H, CH2), 1.30 (s, 18H, C(CH3)3); 13 C NMR (CDCl3, 101 MHz): δ 52.13 (q, 2 JP-C = 11.0 Hz, C(CH3)3), 52.05 (s, N-C), 47.19 (d, 3 JP-C = 10.1 Hz, N-C-CH2), 36.63 (s, CH2), 31.89 (t, 3 JP-C = 7.1 Hz, C(CH3)3), 30.16 (s , N-C-CH2-CH); 31 P-{ 1 H} NMR (CDCl3, 162 MHz): δ 89.2 (s); m.p. 202 °C; IR (mineral oil, NaCl) υ (cm -1 ): 3333 (N-H); MS (EI) m/z: 505.36 [M+1] + ; 2.3.3 -Synthesis of [(p-NHC6H4CN)P(μ-N t Bu)]2 (3.3) Identical to synthetic procedure for 3.1, 1.1 (0.230 g, 0.84 mmol), 4-aminobenzonitrile (0.198 g, 1.7 mmol) and triethylamine (0.24 cm 3 , 1.7 mmol) were used.…”