Synthesis And Characterization Of Thiolate Bridged Multicopper Complexes

Author : Jade Pratt
Publisher :
ISBN 13 : 9781392438800
Total Pages : pages
Book Rating : 4.4/5 (388 download)

DOWNLOAD NOW!

Download or read book Thiols and Tribulations written by Jade Pratt and published by . This book was released on 2019 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In this work we describe the synthesis and characterization of several first row transition metal(II) dithiolates M(SAr[superscript iPr4]2 (Ar[superscript iPr4] = C6H3-2,6-(C6H3-2,6-iPr2)2, M = Cr, Mn, Fe, Co, Ni and Zn and Cr(SAr[superscript Me6])2 (2) (Ar[superscript Me6] = C6H3-2,6-(C6H2-2,4,6-Me3)2) and the ligand transfer reagent (NaSAri[superscript Pr4])2. They are compared to their M(SAr[superscript iPr6])2 (M = Cr, Mn, Fe, Co, Ni, and Zn; Ar[superscript iPr6] = C6H3-2,6-(C6H2-2,4,6-iPr3)2) congeners, which differ by having para-iPr groups on the flanking aryl rings of the terphenyl substituents. These transition metal (II) dithiolates display highly bent coordination geometries with S-M-S angles ranging from 91.730(3)° to 120.2828(3)° as well as relatively close metal-[eta]6 interactions with metal-flanking aryl centroid distances ranging from 1.6206(9) Å to 2.1527(6) Å. However, the d5 (Mn) and d10 (Zn) complexes display linear coordination geometry at the metal atom with no close metal-flanking aryl ring distances. These complexes were generally synthesized by the reaction of a lithium thiolate salt with the metal dihalide, or in the case of Mn(SAr[superscript iPr4])2, by the reaction of the thiol with the amido complex Mn[N(SiMe3)2]2. All compounds were characterized by electronic spectroscopy, X-ray crystallography and magnetic measurements using the Evans’ method and SQUID magnetometry. It was concluded that the absence of para isopropyl groups on the flanking rings of the ligand permit close secondary metal-ring approaches which are favored by the electronic properties of the metal ions. The compounds are characterized by more intense colors and display magnetic moments that are generally lower than the spin only values in agreement with the covalent character of the close metal-aryl ring interactions. The synthesis and characterization of a series of homoleptic copper (I) thiolato complexes (CuSAr[superscript tBu2])4 (Ar[superscript tBu2] = -C6H3-2,6-(C6H4-4-tBu)2), (CuSAr[superscript Me6])4 (Ar[superscript Me6] = -C6H3-2,6-(C6H2-2,4,6-Me3)2) and heteroleptic thiolato copper halides Cu3(SAr[superscript iPr4])2I and Cu3(SAr[superscript iPr6])2Cl are described. The tetrameric species were synthesized by the reaction of one-fourth equivalent of [CuCH2SiMe3]4 to one equivalent of the bulky terphenyl thiol ligands. Cu3(SAr[superscript iPr4])2I was synthesized by the reaction of the copper iodide with the sodium thiolate dimer (NaSAr[superscript iPr4])2 and compound Cu3(SAr[superscript iPr6])2Cl was synthesized by the reaction of the lithium salt, LiSAr[superscript iPr6], with copper chloride. These compounds were characterized by X-ray crystallography and electronic spectroscopy. Additionally, we report a short series of homoleptic tetrametric metal thiolates which were synthesized for silver, (AgSAr[superscript tBu2])4 (Ar[superscript tBu2] = C6H3-2,6-(C6H3-4-tBu2)2), and (AgSAr[superscript Me6])4 (Ar[superscript iPr4] = C6H3-2,6-(C6H3-2,4,6-Me3)2). These compounds were obtained by the reaction of one equivalent of the terphenyl thiolate sodium salt dimer (NaSAr[superscript iPr4])2 with AgOTf and were characterized by X-ray crystallography, IR and NMR spectroscopy.