Reactivity of Zinc Thiolate Bonds: Oxidative Organopolysulfide Formation and S3 Insertion.
Inorg Chem
; 58(16): 10501-10507, 2019 Aug 19.
Article
in En
| MEDLINE
| ID: mdl-31247870
ABSTRACT
Zinc thiolate bonds are intriguing targets of study because of their redox noninnocence and prevalence in bioinorganic sites. A five-coordinate zinc dithiolate complex [Et4N]2[LZn] (H4L = N,N'-di(2-sulfhydrylphenyl)-pyridine-2,6-dicarboxamide) was synthesized to study the oxidative reactivity of zinc thiolate bonds. Multiple chemically reversible reactions of the zinc thiolate bonds were identified. Oxidation of [Et4N]2[LZn] with iodine resulted in structural rearrangement to a bimetallic disulfide-bridged complex. In contrast, the addition of elemental sulfur to [Et4N]2[LZn] resulted in the insertion of a neutral S3 fragment into the Zn-thiolate bond to selectively form an unusual monometallic tetrasulfanido complex. When oxidized, this tetrasulfanido compound rearranged to form a bimetallic trisulfide-bridged complex. The observed diversity of zinc thiolate reactivity, particularly with sulfur, is likely important in biological contexts.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Sulfhydryl Compounds
/
Sulfides
/
Sulfur
/
Zinc
/
Coordination Complexes
Type of study:
Risk_factors_studies
Language:
En
Journal:
Inorg Chem
Year:
2019
Document type:
Article
Affiliation country:
Estados Unidos