Thionitrite and Perthionitrite in NO Signaling at Zinc

Abstract

NO and H₂ 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 H₂ S 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,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(ClO₄ ) provides ^Ph,Me TpZn(SSNO) that undergoes S-atom removal by PEt₃ to give ^Ph,Me TpZn(SNO) and S=PEt₃ . 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 C₆ F₅ SH to form N₂ 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.

Keywords: S-nitrosothiol; bioinorganic chemistry; nitric oxide; thionitrite; zinc.