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Stereoselective Synthesis and Structure of New Types of Calix[4]resorcinarenes. Complexation of Tetrakis( O , O ‐Phosphorus)Bridged‐Calix[4]resorcinarenes with Heavy Metal Atoms
Author(s) -
Sakhaii Peyman,
Neda Ion,
Freytag Matthias,
Thönnessen Holger,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 2000
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(200005)626:5<1246::aid-zaac1246>3.0.co;2-f
Subject(s) - chemistry , resorcinarene , isobutyraldehyde , resorcinol , calixarene , cyclophane , crystallography , crystal structure , stereochemistry , square pyramidal molecular geometry , cyclohexane conformation , catalysis , organic chemistry , molecule , hydrogen bond
The acid‐catalyzed (with HCl) condensation reactions of resorcinol ( 1 ) with 1‐naphthaldehyde ( 2 ) and isobutyraldehyde ( 3 ) furnished the tetrameric macrocyclic compounds 4 and 6 . Detailed NMR‐investigations of the acetylated tetrameric species 5 surprisingly support a structure not in agreement with the expected all‐cis conformation. The chair conformation ( C 2h symmetry) of the acetylated derivative 5 was established through a crystal X‐ray diffraction study. The naphthyl substituents are arranged in trans position above and below the plane made up by the resorcinol units. The reaction of resorcinol 1 with isobutyraldehyde, in accord with expectation, led to the calix[4]resorcinaren ( 6 ). The 1 H NMR spectra of compound 6 and 7 appeared at room temperature as broad signals, indicating a conformation of C 2v symmetry. The reaction of the C‐methyl‐tetrakis‐P‐(chlorodioxaphosphocin)‐calix[4]resorcinarenes ( 8 ) and ( 10 ) with suitable N‐trimethylsilyl organic amines were conducted in tetrahydrofuran suspension, furnishing the P–N‐substituted calix[4]resorcinarenes ( 9 ) and ( 11 ). While in the complexation of C‐methyl‐tetrabromotetrakis‐P‐(dimethylaminodioxaphosphocin)‐calix[4]resorcinarene ( 13 ) with (tht)AuCl (tht = tetrahydrothiophene) the expected, neutral tetra‐substituted complex 15 was formed, the reaction of 13 with moist acetonitrile led to the anionic atomic framework 14 . X‐ray structure determinations of the complexes 14 and 15 show that both possess the cone conformation. In the gold complex 15 , the Au–Cl groups form a loose aggregate, with three Au…Cl contacts of 316–340 pm; one of the groups points towards the centre of the cone. The copper(I) complex 14 displays crystallographic mirror symmetry, with a central Cu 4 Cl 5 unit involving tetrahedrally coordinated copper.