PNP-Perthionitrit und PNP-Monothionitrit / PNP-Perthionitrite and PNP-M onothionitrite

Abstract

<jats:title>Abstract</jats:title><jats:p> As a major product from the reaction of PNP-nitrite [P = P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub>] with elementary sulfur or a PNP-polysulfide (PNP)<jats:sub>2</jats:sub>S<jats:sub>12</jats:sub> in acetone under anaerobic conditions PNP-perthionitrite (PNPnitrosodisulfide) PNP-SSNO has been isolated. VIS/UV-spectra point to a thionitrate or perthionitrate as a precursor. </jats:p><jats:p>The structures of PNP-SSNO and of the product obtained on treating the perthionitrite with triphenylphosphane in acetonitrile, PNP -SNO (PNP-monothionitrite, PNP-nitrososulfide), have been elucidated through X-ray diffraction and independently from new chemical and NMRspectrometric arguments. PNP-SSN O crystallizes in the orthorhombic space group P ben with a = 11.843(3), b = 16.647(5), c = 15.556(4) Å , PNP -SNO in the triclinic group P1̄ with a = 10.525(3), b = 17.196(5), c = 9.451(3) Å , a = 95.22(3), β = 92.32(3), γ = 91.65(3)°.</jats:p>

Chemical foundations of hydrogen sulfide biology

“…Compared with previous reports [285,286], this spectrum was assigned to a hydrodisulfide ONSSH/ONSS − [284]. One speculated mechanism involves an initial nucleophilic attack of H 2 S on RSNO forming HSNO/ − SNO (eq.…”

Nitrosopersulfide (SSNO − ) decomposes in the presence of sulfide, cyanide or glutathione to give HSNO/SNO − : consequences for the assumed role in cell signalling

“…When studying the reaction of S-nitrosoglutathione with H 2 S, at pH 7.4 we observed the formation of yellow product with absorbance at 412 nm but because the time-resolved 15 N NMR studies and time-resolved IR studies confirmed that the 15 N NMR signal and N ¼ O vibrational band, respectively, were only present for short amount of time, while the 'yellow' product remained stable for couple of hours (slowly decaying with sulfur precipitation), we proposed that this is a mixture of polysulfides/sulfur sols [13,36]. Working with pure SSNO 2 we could not test whether there was a water-induced hypsochromic shift, as PNP þ SSNO 2 , as in the Seel's report [32], decomposed when 10% of water was added into the acetone solution of the salt [36]. The matured mixture of GSNO and H 2 S, called 'SSNO 2 mix', has been referred to as enriched SSNO 2 in several papers [35,40 -42], solely based on 412 nm absorbance, although no real chemical evidence was provided to prove that this 'yellow' mixture consists of SSNO 2 .…”

Fundamental chemistry of binary S,N and ternary S,N,O anions: analogues of sulfur oxides and N,O anions

“…A versatile approach to the preparation of salts of binary S,N and ternary S,N,O anions in high yields entails the reactions of silylated derivatives with potassium t-butoxide in ether solvents such as tetrahydrofuran (THF) or boiling dimethoxyethane (DME), as exemplified by the high-yield syntheses of K [NSO] and K2 [NSN] reported by Armitage and Herberhold, respectively; 1, 2 this process is favoured by the formation of the strong Si-O bond in the Me3SiO t Bu by-product [eqn (1) and 2]. Other alkali-metal salts M[NSO] (M = Na, Rb, Cs) have also been prepared by the method shown in eqn (1), 18 while Mews accomplished the synthesis of the soluble tris(dimethylamino)sulfonium (TAS) salt in liquid SO2; the latter transformation is driven by the elimination of volatile trimethylsilyl fluoride [eqn (3)]. 19 KO t Bu + Me3SiNSO…”

“…For example, Seel demonstrated that the red anion SSNOanion is produced by the reaction of an ionic nitrite such as KNO2 with elemental sulfur or a polysulfide in acetone, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) and can be isolated as the PPN + salt (Section 4). 3 Thirty years later Filipovic et al re-investigated this synthesis using K 15 NO2, which allows monitoring the progress of the reaction by 15 N NMR spectroscopy (Section 3.1). A resonance at -67 ppm (cf.…”