Molecular structure and reactivity of a copper(I) tetramer

Abstract

A homoleptic copper(1) tetramer, [Cu(PhTt)14 1, is synthesized using phenyltris[(methylthio)methyl)]borate, PhTt-; X-ray analysis shows the four copper ions are nearly coplanar and each resides in an approximately tetrahedral environment; although 1 is stable towards 0 2 , H 2 0 and CO, it reacts with PPh3, pyridine, or [NEt4]SPh to yield the corresponding monomer, [Cu(PhTt)L] (L = PPh3 2, py 3, [NEt4]SPh 4).

Synthesis, Molecular Structure, and Physical Properties of the Complexes [{PhB(pz)2(CH2SMe)}2M] (M = MnII, FeII; pz = pyrazol‐1‐yl) Containing a Novel [N,N,S]‐Heteroscorpionate Ligand

“…Up to this point our theoretical findings reproduce the trend in solution magnetic moments along the series [N 6 ] to [S 6 ], but clearly not the markedly different monotonous increase of the magnetic moments in the solid state. Given the suspiciously close experimental values obtained for [S 6 ] in solution and in the solid state, we conjectured that the severe disorder present in the crystal lattice could have a non-negligible influence on the solid-state magnetic moment. While we initially assumed that the reason for the disorder was a mere superposition of two meso molecules, we found that the presence of a rac stereoisomer (cf.…”

“…The sample was placed in an Oxford bath cryostat. 6 ] as supporting electrolyte. A 2 mm diameter Pt-disc working electrode was used for 2 and a 3 mm GC-disc working electrode for 3.…”

Synthetic Bioinorganic Chemistry: Scorpionates Turn 50

“…In agreement with Pearson's hard and soft acids and bases (HSAB) principle [107], these ligands should have a good affinity for late transition metals in low oxidation states. Hence, many interesting nickel(I) and copper (I) complexes thereof have been isolated since then, including a tetranuclear compound [Cu(PhTt Me )] 4 [108] and pseudotetrahedral derivatives (PhTt R )Ni (L) (R¼Bu t , Ad; L¼CO, PMe 3 ) [109,110]. In the context of bioinorganic chemistry, the zinc phenylthiolate complex (PhTt tBu ) ZnSPh [111] was synthesized and characterized by X-ray diffraction as a structural model for the active site of the homocysteine-bound forms of methionine synthase enzymes [112,113].…”

Coordination chemistry of poly(thioether)borate ligands

“…Efforts to prepare [PhTt] 2 Cu via similar ligand exchange reactions invariably led to bleaching of the solutions, an indication of metal reduction [38]. Indeed, we have been successful in preparing a wide range of copper(I) derivatives supported by the tris(thioether)borate ligands using copper(I) synthons [39].…”

“…For example, [(PhTt)Cu] 4 and [(Ph 2 Bt)Cu] 4 exist in the solid state and in solution (non-coordinating solvents) as a tetramers with terminal and bridging thioethers (Fig. 4) [38,39]. Alternatively, [PhTt Ph ]Cu and [PhTt pTol ]Cu form extended chain solid state structures lacking bridging thioether ligands because the larger sulfur substituents preclude bridge formation [40].…”