Zinc(II) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-Picoline or 2,4-Lutidine) and [Zn{SSi(OBut)3}2(NH3)2] · MeCN Complexes

Abstract

Zn{SSi(OBu t ) 3 } 2 (NH 3 )] 2 (1) reacts with 2-picoline or 2,4-lutidine (L) without elimination of ammonia giving stable monometallic complexes [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (3 and 4), with two different nitrogen ligands bonded to the metal center. Reaction of (Bu t O) 3 SiSH with zinc di(acetylacetonate) in ammonia atmosphere leads to the complex with two ammine ligands [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´MeCN (5). Molecular and crystal structures of 3, 4 and 5 have been determined by the single crystal X-ray structural analysis. All have distorted tetrahedral geometry. The presence of ammonia gives rise to hydrogen bonds, different in all three cases. 3, 4, and 5 are the first examples of structurally characterized ammine ligated zinc thiolates.Beitra È ge zur Chemie der Silicium±Schwefel Verbindungen. 76. Zink(II) Tri-tert-butoxysilanthiolate. Darstellung, Eigenschaften, Kristallund Moleku È lstrukturen von [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (L = 2-Picolin oder 2,4-Lutidin) und [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´MeCN Inhaltsu È bersicht. [Zn{SSi(OBu t ) 3 } 2 (NH 3 )] 2 (1) reagiert mit 2-Picolin oder 2,4-Lutidin (L) ohne Eliminierung von Ammoniak unter Bildung von stabilen monometallischen Komplexen [Zn{SSi(OBu t ) 3 } 2 (NH 3 )L] (3 und 4), mit zwei verschiedenen stickstoffhaltigen Liganden am Metall-Zentrum. Eine Umsetzung von (Bu t O) 3 SiSH mit Zink-Acetylacetonat in einer Atmospha È re von Ammoniak ergab einen Komplex mit zwei Ammoniak-Liganden [Zn{SSi(OBu t ) 3 } 2 (NH 3 ) 2 ]´M eCN (5). Die Moleku È l-und Kristallstrukturen von 3, 4 und 5 wurden ro È ntgenographisch bestimmt. Alle Verbindungen zeigen eine Abweichung von einer tetraedrischen Geometrie. Die Anwesenheit von Ammoniak fu È hrt zu Wasserstoffbru È ckenbindungen die sich in alle drei Fa È llen unterscheiden. Verbindungen 3, 4 und 5 sind die ersten, strukturell charakterisierten Zink-Thiolate in welchen Zink noch an Ammoniak gebunden ist.

Synthesis, spectroscopy and crystal structure determination of heteroleptic cobalt(II) silanethiolates with pyridine derivatives

“…The molecular structure of (2) based on a tetrahedral CoN 2 S 2 core is distorted as a result of the spatial arrangement of two silanethiolate residues and two 3-methylpyridine molecules with side to side arrangement of the rings. Co-based angles differ from the ideal tetrahedral geometry and vary from 94.24°to 112.12°, without significant influence on the Co-N, Co-S and Si-S bonds lengths, which are not significantly longer then those found in other tetrahedral Co(II) and Zn(II) silanethiolates as previously presented [17,18,21,26]. …”

“…In this range, the spectra contain at least two superimposed bands with varying intensities. In metal silanethiolates, where oxygen from the Si-O-t Bu residue interacts with the metal center, a broad band is observed at about a 980 cm -1 [21][22][23][24][25] (Figs. 8, 9), whereas the spectra of tetrahedral complexes (2) and (4) do not have a characteristic band for O to metal chelating, and only strong asymmetric m (Si-O-C) bands are present at about 1,010 cm -1 .…”

“…The location of the methyl group on the pyridyl ring does not strongly affect the Co-N, Co-S and Si-S bond lengths, which are in the range of those present in other Co(II) and Zn(II) silanethiolates [15,[20][21][22][23][24]. It also does not influence significantly the S(1)-Co(1)-S(2), S(1)-Co(1)-N(1) and S(2)-Co(1)-N(1) angles, which deviate from the ideal 120°, but their sum is very close to 360°(359.99°in both complexes).…”

“…For many years, we have been involved in the synthesis of metal silanethiolates with tri-tert-butoxysilanethiol ( t BuO) 3 SiSH as a thiolate ligand [16][17][18][19][20][21][22][23][24][25][26][27][28]. This compound contains a Si-S bond and bulky tri-tert-butoxyl residues, which provide steric hindrance on the sulfur atom, so protecting the silanethiol against hydrolysis.…”

Manganese(II) tri-tert-butoxysilanethiolate complexes with imidazole-based coligands: A neutral complex with four independent ligands and MNOS2 core (M=Mn) related to the liver alcohol dehydrogenase catalytic center (M=Zn)

“…During investigations of thiolate complexes with bulky and hydrolytically stable ligand derived from tri-tert-butoxysilanethiol (Bu t O) 3 SiSH [16] we prepared compounds with three different ligands -silanethiolate, 2-methylpyridine and ammonia -½MfSSiðOBu t Þ 3 g 2 ðNH 3 Þð2-MePyÞ (M = Zn, Co) [17,18] and detected the formation of complexes with water or alcohol as fourth ligand ½CofSSiðOBu t Þ 3 g 2 ðLÞð2-MePyÞ (L = H 2 O or MeOH) although these could not be isolated [18]. LADH retains 70% of its activity, when Zn is exchanged for Co II [4].…”