Dataset Information

Synthesis and Characterization of Thiolate-Oxo Ligated Zinc Alkyl Derivatives for Production of Zn-Based Nanoparticles.

ABSTRACT: A series of mercapto-oxo containing reagents [3-mercaptopropionic acid (H2-3MPA), 4-mercaptophenol (H2-4MP), 2-mercaptopyridine-N-oxide (H-2MPO)] was reacted with diethyl zinc (ZnEt2) in hexanes/pyridine (py) to yield {(?4-3MPA)[Zn(Et)(py)]4}? (1), [(py)2(Et)Zn(?3-4MP)Zn(Et)(py)]2 (2), and (2MPO)Zn(Et)py (3). For polymeric 1, each of the functional sites of the 3MPA was bound to four tetrahedral (Td) coordinated Zn(Et)(py) subunits. The sulfur of the 3MPA bridges two of the 'Zn(Et)(py)' subunits, which are also bridged by the two carboxylate oxygens of another 3MPA to propagate the chain. In contrast, 2 forms a discrete tetranuclear species consisting of two Zn(Et)(py) moieties bridged by the oxygens of two 4MP ligands with the thiolate sites of each terminated by Zn(Et)(py)2 moieties. Compound 3 adopts a monomeric species using a chelating 2MPO, a terminal Et, and a bound py to fill the Td coordination of the Zn metal center. Compounds 1 - 3 were then used to generate nanoparticles via solution precipitation and solvothermal routes to determine the effect these precursors have on the morphology and composition of the final materials produced. Compounds 1 - 3 were found to form zincite, zinc metal, or mixed zincite/wurtzite phases from solution precipitation or solvothermal routes; however, no routes yielded the mixed anion (i.e., ZnO x S y ) materials.

SUBMITTER: Boyle TJ

PROVIDER: S-EPMC3780448 | biostudies-literature | 2009 Mar

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of Thiolate-Oxo Ligated Zinc Alkyl Derivatives for Production of Zn-Based Nanoparticles.

Boyle Timothy J TJ Pratt Harry D HD Alam Todd M TM Headley Thomas T Rodriguez Mark A MA

European journal of inorganic chemistry 20090301 7

A series of mercapto-oxo containing reagents [3-mercaptopropionic acid (H2-3MPA), 4-mercaptophenol (H2-4MP), 2-mercaptopyridine-N-oxide (H-2MPO)] was reacted with diethyl zinc (ZnEt2) in hexanes/pyridine (py) to yield {(μ4-3MPA)[Zn(Et)(py)]4}∞ (1), [(py)2(Et)Zn(μ3-4MP)Zn(Et)(py)]2 (2), and (2MPO)Zn(Et)py (3). For polymeric 1, each of the functional sites of the 3MPA was ...[more]

PMID: 24068879

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Project description:A series of five-coordinate thiolate-ligated complexes [M(II)(tren)N4S(Me2)]+ (M = Mn, Fe, Co, Ni, Cu, Zn; tren = tris(2-aminoethyl)amine) are reported, and their structural, electronic, and magnetic properties are compared. Isolation of dimeric [Ni(II)(SN4(tren)-RS(dang))]2 ("dang"= dangling, uncoordinated thiolate supported by H bonds), using the less bulky [(tren)N4S](1-) ligand, pointed to the need for gem-dimethyls adjacent to the sulfur to sterically prevent dimerization. All of the gem-dimethyl derivatized complexes are monomeric and, with the exception of [Ni(II)(S(Me2)N4(tren)]+, are isostructural and adopt a tetragonally distorted trigonal bipyramidal geometry favored by ligand constraints. The nickel complex uniquely adopts an approximately ideal square pyramidal geometry and resembles the active site of Ni-superoxide dismutase (Ni-SOD). Even in coordinating solvents such as MeCN, only five-coordinate structures are observed. The MII-S thiolate bonds systematically decrease in length across the series (Mn-S > Fe-S > Co-S > Ni-S approximately Cu-S < Zn-S) with exceptions occurring upon the occupation of sigma* orbitals. The copper complex, [Cu(II)(S(Me2)N4(tren)]+, represents a rare example of a stable CuII-thiolate, and models the perturbed "green" copper site of nitrite reductase. In contrast to the intensely colored, low-spin Fe(III)-thiolates, the M(II)-thiolates described herein are colorless to moderately colored and high-spin (in cases where more than one spin-state is possible), reflecting the poorer energy match between the metal d- and sulfur orbitals upon reduction of the metal ion. As the d-orbitals drop in energy proceeding across the across the series M(2+) (M= Mn, Fe, Co, Ni, Cu), the sulfur-to-metal charge-transfer transition moves into the visible region, and the redox potentials cathodically shift. The reduced M(+1) oxidation state is only accessible with copper, and the more oxidized M(+4) oxidation state is only accessible for manganese.

Dataset Information

Synthesis and Characterization of Thiolate-Oxo Ligated Zinc Alkyl Derivatives for Production of Zn-Based Nanoparticles.

Publications

Synthesis and Characterization of Thiolate-Oxo Ligated Zinc Alkyl Derivatives for Production of Zn-Based Nanoparticles.

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