Structure and physical properties of several pseudotetrahedral zinc complexes containing a new alkyl thiolate heteroscorpionate ligand

Abstract

A series of pseudotetrahedral and octahedral zinc() complexes of the heteroscorpionate ligand bis(3,5-dimethylpyrazolyl)(1-methyl-1-sulfanylethyl)methane (L3SH) have been synthesized and most characterized by X-ray crystallography. Pseudotetrahedral complexes isolated includeand [Zn(L3S) 2 ]. In addition, the octahedral complex [Zn 2 {(L3S) 2 Zn}{O 2 P(OPh) 2 } 4 ] was also synthesized. Comparisons between these complexes and those of the corresponding tris(pyrazolyl)borate, Tp Ϫ , or aromatic phenol or benzenethiolate ligands (L1O) Ϫ and (L2S) Ϫ reveal significant differences. Among these is a change in binding of acetate from pure unidentate to anisobidentate as the ligand donor is changed from S to N to O. Trends such as these may aid in understanding how the donor set affects the structure and reactivity at pseudotetrahedral zinc centers in metalloproteins.

Zinc Thiolate Complexes of (N,N,S)‐Tridentate Ligands for the Modeling of Thiolate Alkylating Enzymes

“…[13] The Zn-N and Zn-S distances of the L 3 ·Zn-SR complexes are in the normal range, comparing well with those both in (N 2 Schelate) [12][13][14] and in (N 2 S-tripod)Zn-SR complexes. [23,24] The coordination pattern of zinc in complexes 3 is close enough to that in the thiolate alkylating enzymes to justify the investigation of alkylating reactions. They were performed for 3d-f using methyl iodide and for 3d using trimethyl phosphate.…”

Dinuclear Zinc Complexes Supported by Macrobinucleating Hexaaza‐Dithiophenolate Macrocycles: Synthesis of Zinc Thiolate Complexes with Biologically Relevant N3S and N2SCl Donor Sets

“…Two amine donors are protonated, and both form intramolecular, charge-assisted, bifurcated hydrogen-bonding interactions with the two sulfur atoms and one Cl -ligand. [41][42][43] The most interesting aspect of this structure is the presence of the ZnN 2 SCl unit with an active coordination site. Only few ZnN 2 SCl complexes have been reported.…”

Electronic effects on the reaction mechanism of the metalloenzyme peptide deformylase

“…Taking advantage that the heteroscorpionate ligand L ( Fig. 2) can be readily substituted along the pyrazolyl groups [22], computations are carried out with a variety of disubstituted biomimetic ligands L, in which both substituents are varied simultaneously and identically. Substituents utilized include electron-withdrawing (-NO 2 , -CN, -CClF 2 , -F) and electron-donating (-i-Pr, -CH 3 , -OCH 3 , -OCH(CH 3 ) 2 , -N=CHC 6 H 5 , -NHCH 3 , -N(CH 3 ) 2 ) groups, with Hammett σ p parameters 1 ranging from +0.78 (most electron-withdrawing) to −0.83 (most electron-donating) [23].…”