Abstract

AbstractNO and H2S serve as signaling molecules in biology with intertwined reactivity. HSNO and HSSNO with their conjugate bases −SNO and −SSNO form in the reaction of H2S with NO as well as S‐nitrosothiols (RSNO) and nitrite (NO2−) that serve as NO reservoirs. While HSNO and HSSNO are elusive, their conjugate bases form isolable zinc complexes Ph,MeTpZn(SNO) and Ph,MeTpZn(SSNO) supported by tris(pyrazolyl)borate ligands. Reaction of Na(15‐C‐5)SSNO with Ph,MeTpZn(ClO4) provides Ph,MeTpZn(SSNO) that undergoes S‐atom removal by PEt3 to give Ph,MeTpZn(SNO) and S=PEt3. Unexpectedly stable at room temperature, these Zn‐SNO and Zn‐SSNO complexes release NO upon heating. Ph,MeTpZn(SNO) and Ph,MeTpZn(SSNO) quickly react with acidic thiols such as C6F5SH to form N2O and NO, respectively. Increasing the thiol basicity in p‐substituted aromatic thiols 4−XArSH in the reaction with Ph,MeTpZn(SNO) turns on competing S‐nitrosation to form Ph,MeTpZn‐SH and RSNO, the latter a known precursor for NO.

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