1064680-53-0Relevant academic research and scientific papers
Copper complexes of mono- and ditopic [(methylthio)methyl]borates: Missing links and linked systems en route to copper enzyme models
Ruth, Kai,Tuellmann, Sandor,Vitze, Hannes,Bolte, Michael,Lerner, Hans-Wolfram,Holthausen, Max C.,Wagner, Matthias
, p. 6754 - 6770 (2008)
TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH2-SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr2 and its p-silylated derivative Me3Si-C6H 4-BBr2. The resulting compounds, R*-C 6H4-B(Br)-(CH2SMe) (R* = H: 2; R* = SiMe3: 7) and PhB(CH2SMe)2 (3), form cyclic dimers through B-S adduct bonds in solution and in the solid state. Compounds 2 and 3 have successfully been used for preparing the (N2S) scorpionate [PhBpZ2(CH2SMe)]- ([5]-) (pz: pyrazol-1-yl) and the (NS2) scorpionate [PhBpz(CH2SMe) 2]-, respectively. Compound 7 proved to be an excellent building block for the heteroditopic poly(pyrazol-l-yl)borate p-[pz 3B-C6H4-Bpz2(CH2SMe)] 2- ([10]2-) that mimics the two ligation sites of the copper enzymes peptidylglycine α-hydroxylating monooxygenase and dopamine ss-monooxygenase. Treatment of the monotopic tripod [5]- with CuCl and CuBr2 results in the formation of complexes K[Cu(5) 2] and [Cu(5)2]. An X-ray crystallography study of K[Cu(5)2] revealed a tetrahedral (N2S2) coordination environment for the Cu1 ion, whereas the CuII ion of [Cu(5)2] possesses a square-pyramidal (N4S) ligand sphere (S-atom in the axial position). The remarkable redox properties of K[Cu(5)2] and [Cu(5)2] have been assessed by cyclic voltammetry and quantum chemical calculations. The reaction of K[Cu(5) 2] with dry air leads to the CuII species [Cu(5) 2] and to a tetranuclear CuII complex featuring [PhB(O)pz2]2- ligands. Addition of CuCl to K 2[10] gives the complex K3[Cu(10)2] containing two ligand molecules per Cu1 center. The Cu1 ion binds to both heteroscorpionate moieties and thereby establishes a coordination environment similar to that of the Cu1 ion in K[Cu(5)2].
