Phenyltris((tert-butylthio)methyl)borate:  A Second Generation S₃^- Ligand That Enforces Tetrahedral Coordination

Abstract

The preparation of the new S3 -, tetrahedral enforcer ligand, PhTt t -Bu- (phenyltris((tert-butylthio)methyl)borate), is reported as the Tl(I) salt along with its corresponding [PhTt t -Bu]CoCl and [PhTt t -Bu]NiCl complexes. Each has been characterized by X-ray diffraction. Preliminary reactivity studies demonstrate that [PhTt t -Bu]NiCl is a useful synthon for the preparation of a range of tetrahedral derivatives.

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

“…The copper complexes K [11] and 12 (Scheme 3) were prepared by the reaction of K[5] with 1.3 equiv of CuCl and 0.5 equiv of CuBr 2 , respectively. Toluene was chosen as the reaction medium, which led to heterogeneous conditions and thus to reaction times of several days.…”

“…Toluene was chosen as the reaction medium, which led to heterogeneous conditions and thus to reaction times of several days. The solubility of K [5] in toluene is higher than the solubility of CuCl, thus promoting the formation of complexes of stoichiometry K[Cu(5) 2 ] (i.e., K [11]), even though the ratio of the starting materials was roughly 1:1. Samples prepared in solvents other than toluene did not provide single crystalline-A C H T U N G T R E N N U N G material.…”

“…We therefore investigated the behavior of K [11] towards dry molecular oxygen in C 6 H 6 solution at room temperature. From the paramagnetic reaction mixture, crystals were grown of the Cu II complex 12 (major component) and of a degradation product 13 containing [PhBpz 2 (O)] 2À ligands (minor component; Scheme 3).…”

“…From the paramagnetic reaction mixture, crystals were grown of the Cu II complex 12 (major component) and of a degradation product 13 containing [PhBpz 2 (O)] 2À ligands (minor component; Scheme 3). The oxidative cleavage of the BÀC bond indicates activation of O 2 by K [11] in a manner reminiscent of related enzyme-mediated processes. The heterodinuclear complex 14 (Scheme 3) was synthesized from K 2 [10] and CuCl in THF (stoichiometric ratio = 1:3).…”

Hoch oder niedrig? Zur Erlaubtheit von Spinzuständen in der Übergangsmetallchemie

“…Beim Tetraeder (T-ML 4 ) scheiden die beiden Spinzustände S = 3/2 und S = 1/2 aus, weil die Energiedifferenz zwischen den e-und t 2 [28,29] (1-3, Abbildung 8), z. B. ein Tripyrazolylborat (E = N), [30] Triphosphanborat (E = P), [31,32] Trithioborat (E = S) [33] oder Tris-(carben)borat. [34] Diese Verbindungen haben Low-Spin-Konfiguration, wenn der vierte Ligand X ein p-Donor ist.…”