The study demonstrates the synthesis and reactivity of stable zinc thionitrite and perthionitrite complexes, providing insights into NO and H2S signaling mechanisms.
Zinc complexes of SNO/SSNO enable NO/H2S signaling studies; leaves open cardiovascular relevance pending biological validation.
NO and H 2 S serve as signaling molecules in biology with intertwined reactivity. HSNO and HSSNO with their conjugate bases − SNO and − SSNO form in the reaction of H 2 S with NO as well as S‐nitrosothiols (RSNO) and nitrite (NO 2 − ) that serve as NO reservoirs. While HSNO and HSSNO are elusive, their conjugate bases form isolable zinc complexes Ph,Me TpZn(SNO) and Ph,Me TpZn(SSNO) supported by tris(pyrazolyl)borate ligands. Reaction of Na(15‐C‐5)SSNO with Ph,Me TpZn(ClO 4 ) provides Ph,Me TpZn(SSNO) that undergoes S‐atom removal by PEt 3 to give Ph,Me TpZn(SNO) and S=PEt 3 . Unexpectedly stable at room temperature, these Zn‐SNO and Zn‐SSNO complexes release NO upon heating. Ph,Me TpZn(SNO) and Ph,Me TpZn(SSNO) quickly react with acidic thiols such as C 6 F 5 SH to form N 2 O and NO, respectively. Increasing the thiol basicity in p‐substituted aromatic thiols 4−X ArSH in the reaction with Ph,Me TpZn(SNO) turns on competing S‐nitrosation to form Ph,Me TpZn‐SH and RSNO, the latter a known precursor for NO.
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Hosseininasab et al. (2021) studied this question.
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