S-nitrosothiol and nitric oxide reactivity at β-diketiminato zinc thiolates

Synthesis of a “Masked” Terminal Zinc Sulfide and Its Reactivity with Brønsted and Lewis Acids

“…Addition of 1 equivalent of KSCPh 3 to [ Me LZnCl] in THF results in the formation of [ Me LZn(SCPh 3 )] ( 1 ), which can be isolated in 85 % yield after work‐up (Scheme ). In the solid state, 1 crystallizes with two independent molecules in the asymmetric unit (Figure S21 in the Supporting Information) and its metric parameters mirror those found in the closely related Zn trityl thiolate, [ Me* LZn(SCPh 3 )] ( Me* L={(2,6‐Me 2 C 6 H 3 )NC(Me)} 2 CH), reported by Warren and Varonka . For instance, the Zn–S distances in 1 are 2.212(3) and 2.191(3) Å, whereas this distance in [ Me* LZn(SCPh 3 )] is 2.2142(6) Å.…”

“…In the solid state, 1 crystallizes with two independent molecules in the asymmetric unit ( Figure S21 in the Supporting Information) and its metric parameters mirror those found in the closely related Zn trityl thiolate, [ Me* LZn(SCPh 3 )] ( Me* L = {(2,6-Me 2 C 6 H 3 )NC(Me)} 2 CH), reported by Warren and Varonka. [21] For instance, the Zn-S distances in 1 are 2.212(3) and 2.191(3) , whereas this distance in [ Me* LZn(SCPh 3 )] is 2.2142 (6) . In addition, complex 1 has been characterized by 1 H and 13 C{ 1 H} NMR spectroscopy and elemental analysis.…”

OO Bond Activation in Heterobimetallic Peroxides: Synthesis of the Peroxide [LNi(μ,η2:η2‐O2)K] and its Conversion into a Bis(μ‐Hydroxo) Nickel Zinc Complex

“…As expected, the OÀO separation of 1.468 (2) is significantly longer than the value observed in the superoxo ligand in 1 (1.347 (2) ) but similar to the distances observed for other metal peroxo complexes (1.4-1.5 ). To probe whether the K + ion can be replaced by another non-redox-active center under retention of the peroxo moiety, we performed the reaction of 2 a with the (b-diketiminato)zinc(II) chloride LiCl adduct [L'Zn(m-Cl) 2 Li(thf) 3 ] [12] as precursor for [L'ZnCl] in THF at ambient temperature. [9b] Although the potassium center is coordinated to the six oxygen atoms of the crown ether and additionally to one oxygen atom of the adjacent [18]c-6 ligand, it is also tightly coordinated to both peroxide oxygen atoms (O1, O2), with K1ÀO1 and K1ÀO2 separations of 2.695(2) and 2.734(2) , respectively.…”

OO Bond Activation in Heterobimetallic Peroxides: Synthesis of the Peroxide [LNi(μ,η2:η2‐O2)K] and its Conversion into a Bis(μ‐Hydroxo) Nickel Zinc Complex

“…Remarkably, attempts to separate the K + ion from the peroxide oxygen atoms (formation of ion pairs) have been unsuccessful, and not even the powerful [2,2,2] cryptand was capable of cleaving the K À O 2 contact. To probe whether the K + ion can be replaced by another non-redox-active center under retention of the peroxo moiety, we performed the reaction of 2 a with the (b-diketiminato)zinc(II) chloride LiCl adduct [L'Zn(m-Cl) 2 Li(thf) 3 ] [12] as precursor for [L'ZnCl] in THF at ambient temperature. To our surprise, the cation replacement led to the bis(m-hydroxo) Ni II (OH) 2 Zn II complex 3 instead of the expected analogous peroxo complex, which can be isolated in the form of brown crystals in 42 % yield (Scheme 1).…”