Cobalt(II) Tri‐ tert ‐butoxysilanethiolates with Bidentate Spacer Ligands

A new series of Co II tri‐ tert ‐butoxysilanethiolate complexes with bidentate N , N′ ‐ligands (L) such as pyrazine, quinoxaline and 4,4′‐bipy was obtained: for pyrazine and quinoxaline the complexes are binuclear {[Co{SSi( t BuO) 3 } 2 ] 2 (μ‐L)} with metal atoms linked by an adequate heterocyclic base L. The use of 4,4′‐bipy resulted in a coordination polymer [Co{μ‐SSi( t BuO) 3 }{SSi( t BuO) 3 }(μ‐4,4′‐bipy)] n and two polymorphic forms of {[Co{SSi( t BuO) 3 } 2 ] 2 (μ‐4,4′‐bipy)}. Pyridyl rings in one polymorph form a torsion angle of 0.57°, whereas a rotation about the linking C–C bond of 4,4′‐bipy in second polymorph is significant and results in a torsion angle of 72.4°. Complexes were analysed and characterised using elemental analysis, solid state IR and UV/Vis spectroscopy, and single‐crystal X‐ray analysis.