A Tripodal Trisilanol Ligand and Its Complexation Behavior towards Cu^I, Cu^II, and Zn^II

Abstract

A three-step synthetic route for a new tripodal branched trisilanol ligand PhSi(OSiPh 2 OH) 3 (LH 3 ) was developed. X-ray diffraction analysis revealed that the trisilanol crystallizes as a dimer with a cyclic hydrogen-bonding network. The reaction of LH 3 with three equivalents of Cu n Mes n (Mes = mesityl) led to a hexanuclear compound [L 2 Cu 6 ] (1), which was characterized by single-crystal X-ray diffraction analysis as well as by solution NMR spectroscopy. The crystal structure of 1 revealed that the compound features a hexagonal planar Cu I 6 ring, which is the first of its kind in an oxygen environ-[a] Humboldt-

Preparation of Siloxane‐Based Microporous Crystals from Hydrogen‐Bonded Molecular Crystals of Cage Siloxanes

“…which is in clear contrastt ot he previously reported crystalso f organosilanols that consist of as ingle type of H-bond networks. [11,14] The hexameric cyclic H-bond network was formed by intra-and intermolecular Hb onds between four cage siloxanes in the same layer (Figure 2d,g reen dashed line). Alternatively,t he octameric cyclic H-bond network wasf ormed by in-termolecularHbonds between two cage siloxanes in aface-toface manner (Figure 2d,b lue dashed line).…”

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

“…M a n u s c r i p t When n-BuLi is used to deprotonate 27 in the presence of CuBr 2 , a spirocyclic structure 29 is formed but the siloxane molecule rearranges under these conditions, thereby eliminating cyclic siloxane (Ph 2 SiO) 4 . Interestingly, this does not occur when Zn(II) is used instead of Cu(II), where the reaction yields polyhedral structure 30 (Scheme 11) [56].…”

“…In the last step, Si-H groups are transformed into Si-OH by oxidation with methyl(trifluoroethyl)dioxirane. The resulting compound 27 crystallizes as a hydrogenbonded dimer with a prismatic structure (Scheme 9) [56]. M a n u s c r i p t When n-BuLi is used to deprotonate 27 in the presence of CuBr 2 , a spirocyclic structure 29 is formed but the siloxane molecule rearranges under these conditions, thereby eliminating cyclic siloxane (Ph 2 SiO) 4 .…”

“…Synthesis of an incompletely condensed siloxane oligomer.The crystallization of 27 in the presence of Cu(I) yields PHMS 28 with a similar shape (Scheme 10)[56].…”

The Syntheses and Crystal Structures of the First Disiloxane‐1,3‐dithiol and Its Cadmium Complex

“…Such protection allows the isolation of relatively stable, molecular compounds with -OH/SH functional groups attached directly to silicon atoms. [9][10][11][12][13][21][22][23] Monosilanols inhibit bacterial growth. [20] Molecular species possessing Si-O bonds such as silanols, silanediols, disiloxane-1,3-diols, silanetriols, other related species, and their metal salts may serve as structural models for silica-supported metal or metal oxide catalysts.…”