Di-tert-butyl thiopyridazine boratrane complexes of Co, Ni and Cu

Synthesis and Characterization of a Thiopyridazinylmethane-Based Scorpionate Ligand: Formation of Zinc Complexes and Rearrangement Reaction

“…In our group we focus on the synthesis and reactivity of thiopyridazine-based scorpionate ligands. ,,− They show interesting reactivity contrasting with that of other soft scorpionates, as they were found to be photoreactive and prone to the formation of boratrane complexes with the concomitant reduction of the metal center. ,,, This led us to investigate the formation of a carbon-based scorpionate with this heterocycle. The tert -butyl group of the used thiopyridazine might influence the steric hindrance of the formed complexes, while the additional nitrogen atom in the heterocycle might alter the electron-donating properties of the ligand in comparison to its thiopyridine-based analogue.…”

(Acetamide-κO){2,2′,2′′-boranetriyltris[6-tert-butyl-4-methylpyridazine-3(2H)-thione]-κ4 B,S,S′,S′′}copper(I) trifluoromethanesulfonate chloroform disolvate

“…Their Z-type coordination mode provides an entry into electronically interesting metal atoms, which recently were successfully used in catalytic dinitrogen reduction (Anderson et al, 2013). Our group is focusing on thiopyridazine-based soft scorpionates and their related metallaboratrane complexes (Nuss et al, 2011a,b;Holler et al, 2016Holler et al, , 2017. In an attempted synthesis of the boratrane complex {2,2 0 ,2 00 -boranetriyltris[6-tert-butyl-4-methylpyridazine-3(2H)-thione]}(trifluoromethanesulfonato)copper(I) (= [Cu{B(Pn Me,tBu ) 3 }(OTf)]), described in the literature by our group (Holler et al, 2016), the title compound formed serendipitously by reaction with residual acetamide from the acetonitrile solvent.…”

{(Hydrogen 2,2′,2′′-boranetriyl)tris[6-tert-butyl-4-methylpyridazine-3(2H)-thione]-κ3H,S,S′}(triphenylphosphane-κP)copper(I) chloroform disolvate

“…Soft scorpionate ligands have gained significant attention in synthetic inorganic chemistry over the last decades (Spicer & Reglinski, 2009;Reglinski & Spicer, 2015). For some years we have been investigating the behaviour of thiopyridazine-based hydroborates towards various metals and observed preferred metallaboratrane formation (Nuss et al, 2011a,b;Holler et al, 2016Holler et al, , 2017. However, the reaction of our soft scorpionate ligand potassium tris(6-tert-butyl-4-methylpyridazine-3(2H)-thione)borate (= KTn Me , tBu ) with copper(I) chloride in the presence of triphenylphosphane retained the borate ligand and led to the title compound.…”