Cobalt(II) and Cobalt(III) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Co{μ-SSi(OBut)3}{SSi(OBut)3}(NH3)]2 and [Co{SSi(OBut)3}2(NH3)4][SSi(OBut)3] Complexes

Abstract

The heteroleptic neutral tri-tert-butoxysilanethiolate of cobalt(II) incorporating ammonia as additional ligand (1) has been prepared by the reaction of a cobalt(II) ammine complex with tri-tert-butoxysilanethiol in water. Complex 1, dissolved in hexane, undergoes oxidation in an ammonia saturated atmosphere to the ionic cobalt(III) compound 2. Molecular and crystal structures of 1 and 2 have been determined by single crystal X-ray structural analysis. 1 forms a dimeric molecule [Co{l-SSi(OBu t ) 3 }{SSi(OBu t ) 3 }(NH 3 )] 2 with a folded central Co 2 S 2 ring and distorted tetrahedral ligand arrangement at both Co II atoms (CoNS 3 core). The product 2 is composed of the octahedral Co III complex cation [Co{SSi(OBu t ) 3 } 2 (NH 3 ) 4 ] + and the tri-tertbutoxysilanethiolate anion. Within the crystal two pairs of ions interact by hydrogen bonds forming well separated entities. 1 and 2 are the first structurally characterized cobalt thiolates where metal is also bonded to ammonia and 2 is the first cobalt(III) silanethiolate.Beitra È ge zur Chemie der Silicium-Schwefel Verbindungen. 74. Cobalt(II) und Cobalt(III) Tri-tert-butoxysilanthiolate. Darstellung, Eigenschaften, Kristall-und Moleku È lstrukturen von [Co{l-SSi(OBu t ) 3 }{SSi(OBu t ) 3 }(NH 3 )] 2 und [Co{SSi(OBu t ) 3 } 2 (NH 3 ) 4 ][SSi(OBu t ) 3 ]Inhaltsu È bersicht. Das heteroleptische, neutrale, als zusa Ètz-lichen Liganden Ammoniak enthaltende Cobalt(II)-tri-tertbutoxysilanthiolat (1) wurde bei der Umsetzung von Tri-tertbutoxysilanthiol mit einem Cobalt±Ammin-Komplex in wa È sseriger Lo È sung erhalten. Verbindung 1, aufgelo È st in Hexan, oxidiert sich in einer mit Ammoniak gesa È ttigen Atmospha È re zum ionischen Cobalt(III)-Komplex 2. Die Moleku È lund Kristallstrukturen von 1 und 2 wurden ro È ntgenographisch bestimmt. 1 bildet ein dimeres Moleku È l [Co{l-SSi(OBu t ) 3 }{SSi(OBu t ) 3 }(NH 3 )] 2 mit einen gefaltenen Co 2 S 2 Ring und einer fast tetraedrischen Anordnung der Liganden an beiden Co II -Atomen (CoNS 3 Rumpf). 2 ist ionisch aufgebaut mit einem oktaedrischen Co III -Kation [Co{SSi(OBu t ) 3 } 2 (NH 3 ) 4 ] + und einem Tri-tert-butoxysilanthiolat-Anion. Im Kristall sind zwei Paare dieser Ionen durch Wasserstoffbru È cken zu isolierten Einheiten gebunden.

Structural Variety of Cobalt(II), Nickel(II), Zinc(II), and Cadmium(II) Complexes with 4,4′‐Azopyridine: Synthesis, Structure and Luminescence Properties

“…Tri‐ tert ‐butoxysilanethiol, [Co{SSi(O t Bu) 3 } 2 (NH 3 )] 2 , and [Cd{SSi(O t Bu) 3 } 2 ] 2 were synthesized as reported previously . All other starting materials were obtained from commercial sources and were used without further purification.…”

Polymeric cobalt(ii) thiolato complexes – syntheses, structures and properties of 1∞[Co(SMes)2] and 1∞[Co(SPh)2NH3]

“…Amine ligated cobalt complexes with monodentate thiolato ligands SR − are rare and include for example [Co (S-2,4,6-i Pr 3 C 6 H 2 ) 2 (Py) 2 ], 34 35 [Co(SPh) 2 ( p-Tol-NPMe 3 ) 2 ], 36 [Co(SAr) 2 (tmeda)], 37 (Ar = 2,4,6-t Bu 3 C 6 H 2 , tmeda = tetramethylethylenediamine) and [Co(SPh) 2 ( phen)]ClO 4 ( phen = phenanthroline). 38 Only four examples of cobalt thiolato complexes with ammonia ligands have been characterized so far namely [{Co(SSi(O t Bu) 3 ) 2 (NH 3 )} 2 ], 39 [Co(SSi(OAr) 3 ) 2 (NH 3 ) 2 ] (Ar = t Bu, 40 2,6-i Pr 2 C 6 H 3 ) 41 and the cationic Co(III) complex [Co(SSi(O t Bu) 3 ) 2 (NH 3 ) 4 ] + . 39 Herein we report on the synthesis and structural characterization of the first polynuclear thiolato complexes of Co(II) including characterization by UV-vis-NIR spectroscopy, magnetic measurements and thermal gravimetric analysis.…”

“…38 Only four examples of cobalt thiolato complexes with ammonia ligands have been characterized so far namely [{Co(SSi(O t Bu) 3 ) 2 (NH 3 )} 2 ], 39 [Co(SSi(OAr) 3 ) 2 (NH 3 ) 2 ] (Ar = t Bu, 40 2,6-i Pr 2 C 6 H 3 ) 41 and the cationic Co(III) complex [Co(SSi(O t Bu) 3 ) 2 (NH 3 ) 4 ] + . 39 Herein we report on the synthesis and structural characterization of the first polynuclear thiolato complexes of Co(II) including characterization by UV-vis-NIR spectroscopy, magnetic measurements and thermal gravimetric analysis.…”

Bis(tri-tert-butoxysilanethiolato-κS)bis(pyrrolidine-κN)cobalt(II)

“…[Co{SSi(O t Bu) 3 } 2 (NH 3 )] 2 was obtained as described previously by Becker et al (2001a). All other reagents were obtained commercially.…”