Extended Structures Built on a Triphenoxymethane Platform −C3-Symmetric, Conformational Mimics of Calix[n]arenes

Abstract

A series of C 3 -symmetric tris(3,5-dialkyl-2-hydroxyphenyl)-methanes (alkyl = tert-butyl, methyl, tert-pentyl) have been synthesized in high yield from their respective phenols and fully characterized, including single crystal X-ray structures for two examples. The di-tert-butyl-substituted compound, 1a, has been derivatized to a tris-acid chloride, 4, which was treated with a variety of amines (dimethylamine, benzylamine, glycine, and alanine) from which the corresponding trisamides 5−8 were formed. The absolute geometry and conformation of the dimethylamine, glycine, and alanine derived systems were determined by X-ray analyses, and in all cases,

Synthesis and Coordination Properties of Tripodal Ligand on the Triphenylphosphine Oxide Platform with Carbamoyl Side Arms

“…Let us note that the same value for the shift of C O group signal was detected in the 13 C NMR spectra of tripodal ligand on triphenylmethane platform with carbamoyl arms structurally akin to the studied ligand 1. 4 The noted work reports the changes in the frequencies of C O groups in IR spectra upon coordination to metals that are similar to our data. The signals of aryl carbon nuclei C(3) and C(2) are shifted upfield by 0.53 and 0.17 ppm, while the carbon resonances of C(5) and C(4) are shifted downfield by 0.51 and 1.84 ppm, respectively.…”

“…The proton signals of the butyl fragment-CH 3 , CH 3 CH 2 , CH 2 CH 2 N, and CH 2 N-are shifted downfield relative to the signals of the free ligand by 0.05 to 0. 21 The signal of H(6) at ∼7.3 ppm is broadened and shifted upfield by 0.3 ppm owing to the proximity to the coordinated P O group, the signal is slightly overlapped with the signal of residual protons of the solvent.…”

“…6,13,14 Tripodal ligands are generally constructed of a core atom or group (platform) with attached functionalized chains containing donor (or H-bonding) atoms, for example, functionalized trialkylamines, 15 trialkylmethanes, [16][17][18] trialkylphosphines, 19 etc. Tripodal ligands on triarylmethane platform with rigid side groups are of interest in terms of complexation selectivity because they have a propeller conformation where ortho substituents in phenyl rings are oriented to the same direction [20][21][22][23] thus confining the size of bound cation.…”

Structural Diversity of Tris(2‐hydroxy­aryl)methane‐Derived Aluminium Complexes

“…The triphenol ligands (L tBu H 3 [2,13] and L Me′ H 3 [14] ) and B(C 6 F 5 ) 3 [15] were prepared according to literature procedures. 1 H, 13 C, and 31 P NMR spectra were recorded with Varian GEMINI 300, INOVA 400, and Varian 400-MR Fourier-transform spectrometers. 1 H chemical shifts are referenced to the residual proton peaks of [D 6 ]benzene at δ = 7.15 ppm or [D 8 ]tetrahydrofuran at δ = 3.58 ppm versus tetramethylsilane.…”

Advanced Extraction Methods for Actinide/Lanthanide Separations

“…This conformer forces all oxygens on the same site relative to the central methine hydrogen of the platform both in the solid state and in solution. 38 The attachment of three CMPO moieties to this platform through the The CMPO moieties were tethered to the platform using well-established derivatization method developed for the CMPO-calixarene systems (Scheme 2). 32,33 The attachment of the CMPS moieties was facilitated using synthetic methodology developed for preparation of the hydroxypyridinones.…”