A Tripodal Trisilanol Ligand and Its Complexation Behavior towards CuI, CuII, and ZnII. Issue 12 (12th March 2014)

• Record Type: Journal Article
• Authors: Schax, Fabian; Braun, Beatrice; Limberg, Christian
• Is Part Of: European journal of inorganic chemistry. Issue 12(2014)
• Page Start: 2124
• Page End: 2130
• Publication Date: 2014-03-12
• Subjects: Copper -- Zinc -- Metal aromaticity -- Rearrangement -- Siloxides -- Silanols; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201400088
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: A three‐step synthetic route for a new tripodal branched trisilanol ligand PhSi(OSiPh2 OH)3 (L H3 ) was developed. X‐ray diffraction analysis revealed that the trisilanol crystallizes as a dimer with a cyclic hydrogen‐bonding network. The reaction ofL H3 with three equivalents of Cu n Mes n (Mes = mesityl) led to a hexanuclear compound [L 2 Cu6 ] (1 ), which was characterized by single‐crystal X‐ray diffraction analysis as well as by solution NMR spectroscopy. The crystal structure of1 revealed that the compound features a hexagonal planar Cu I 6 ring, which is the first of its kind in an oxygen environment. Deprotonation of the ligand with n ‐butyllithium and subsequent reaction with CuBr2 resulted in the dinuclear Cu II complex [L′ 2 Cu2 ][Li(THF2 )]2 (2, THF = tetrahydrofuran), which contains a new siloxide ligand formed fromL 3– by the elimination of a SiOPh2 unit, as evidenced by X‐ray diffraction analysis. To check if the "Ph2 SiO" elimination is a general behavior of this trisilanol, the reaction with ZnBr2 was investigated under analogous conditions. However, this led to the isolation of [L 2 Zn2 ][Li(OEt)]2 (3 ) without any rearrangement of the siloxide ligand. Abstract : A tripodal branched trisilanol ligand PhSi(OSiPh2 OH)3 (L H3 ) was synthesized. Its reaction with three equivalents of Cu n Mes n (Mes = mesityl) led to a hexanuclear compound [L 2 Cu6 ] with a planar Cu I 6 ring. Deprotonation ofL H3 with n ‐butyllithium and subsequent reaction with either CuBr2 or ZnBr2 resulted in dinuclear complexes. In the case of CuBr2, the original ligand eliminates a "Ph2 SiO" unit.