Synthesis of bis(bora)calix[4]arenes bearing perfluoroaryl substituents

Redshaw, Carl; Elsegood, Mark R. J.

doi:10.1039/b509556e

Cited by 8 publications

(5 citation statements)

References 10 publications

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“…9, 10 Main group calixarene complexes reported in the literature (M = B, As, Al, Ga, Zn, Ge, Sn) are usually prepared by either the parent or ether-substituted calixarenes in reactions with organometals, metal amides or metal alkoxides. 11- 18 Most of these complexes are supported by even numbered calix[n]arene (n = 4 and 8) ligands and the lower rim is usually fully metallated. We, on the other hand, have described the synthesis and characterization of a large series of mono-, di-, tri-, and pentaanionic calixarene alkali metal salts, [19][20][21] and have already demonstrated their utility as an entry into both main group and transition metallocalixarenes (including the first reported antimony calixarene) that were inaccessible using the traditional parent calixarene as the precursor.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, X-ray structures and reactivity of calix[5]arene bismuth(iii) and antimony(iii) complexes

Mendoza‐Espinosa

Hanna

2009

Dalton Trans.

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A series of calix[5]arene bismuth(III) and antimony(III) mono- and bimetallic complexes were synthesized and fully characterized by NMR, X-ray, IR, mp, UV-Vis and elemental analysis. Reaction of p-tert-butylcalix[5]arene (tBuC5(H)5) trianionic salts M'3.tBuC5(H)2 (M'=Li, Na, K) with MCl3 (M=Bi, Sb) yielded monometallic complexes [Bi{tBuC5(H)2}] 1 and [Sb{tBuC5(H)2}] 2, respectively. 1H NMR spectra of both complexes showed two remaining OH groups available for further reactivity. Alternatively, complexes 1 and 2 can be obtained by reacting tBuC5(H)5 in a 1:1 ratio with M(OtBu)3, but the yields are lower. When the tBuC5(H)5 lower rim monobenzyl ether [tBuC5(Bn)(H)4] is treated in a 1:1 ratio with Bi(OtBu)3, the monometallic complex [Bi{tBuC5(Bn)(H)}]2 3 is prepared. If, however, [tBuC5(Bn)(H)4] reacts with Sb(NMe2)3 or Sb(OtBu)3 in a 1:2 ratio the production of the bimetallic complex [Sb2O{tBuC5(Bn)}] 4 is observed. p-Benzylcalix[5]arene (BnC5(H)5) reacts with excess Bi(OtBu)3 to produce the bimetallic complex [Bi2O{BnC5(H)}]2 5. 1H NMR spectra of 5 display patterns characteristic for a cone conformer in solution. Treatment of calix[5]arene [HC5(H)5] with one equivalent of Bi[N(SiMe3)2]3 or with 0.75 equivalents of Sb(NMe2)3 yields bimetallic complexes [Bi2O{HC5(H)}] 6 and [Sb2O{HC5(H)}] 7, respectively. The reactivity of monometallic complexes 1 and 2 was tested in order to investigate the availability of their remaining OH groups. Treatment of 1 with Bi(OtBu)3 at ambient temperature yields bimetallic complex [Bi2O{tBuC5(H)}]2 8 while the reaction of complex 2 with Sb(OtBu)3 in a 1:1 ratio produces complex [Sb2O{tBuC5(H)}] 9. The crystal structures of the monometallic bismuth complexes 1 and 3 display dimeric units with the calixarene ligands in distorted cone and "paco-in" conformations, respectively. Complexes 4, 7 and 9 are all monomeric units, displaying [(RO)2Sb]2(micro-O) cores and the calixarene ligands in 1,2-alternate conformation. The dimeric units of bimetallic complexes 5 and 8 contain Bi4O2(OR)8 core structures that force the calixarene ligands to adopt a flattened cone conformation.

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Section: Introductionmentioning

confidence: 99%

Synthesis, X-ray structures and reactivity of calix[5]arene bismuth(iii) and antimony(iii) complexes

Mendoza‐Espinosa

Hanna

2009

Dalton Trans.

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“…The most common pathway for the preparation of main group calix[ n ]arenes ( n = 4, 6, 8) involves the reaction of the parent calix[ n ]arene ligands with metal amides, organometals, or metal alkoxides in exchange reactions. ,− Lattman et al have shown that monophosphorus substituted ligands of the type t BuC5(PNMe 2 )(H) 3 readily react with transition metal amides (M = Ti, Zr, W) to produce metalated complexes of the type [M{ t BuC5(PNMe 2 ) }]. , We have reported that M(O t Bu) 3 (M = Bi, Sb) or Sb(NMe 2 ) 3 are excellent reagents for the preparation of metallocalix[ n ]arenes ( n = 4−8). ,, …”

Section: Resultsmentioning

confidence: 99%

Facile Synthesis of Bismuth(III) and Antimony(III) Complexes Supported by Silylated Calix[5]arenes.

Mendoza‐Espinosa

Hanna

2009

Inorg. Chem.

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A series of bismuth(III) and antimony(III) complexes supported by silicon-containing calix[5]arene ligands were synthesized and fully characterized by NMR, X-ray, IR, mp, UV/vis, and elemental analysis. Reaction of the para-tert-butylcalix[5]arene [(t)BuC5(H)(5)] disodium salt, Na(2) x (t)BuC5(H)(3), with 1 equiv of R(2)SiCl(2) (R = Me, (i)Pr, Ph, CH=CH(2)) or treatment of the (t)BuC5(H)(5) lower rim monobenzyl ether [(t)BuC5(Bn)(H)(4)] in a 1:1 ratio with Me(2)Si(NMe(2))(2) yields the (t)BuC5(SiRR')(H)(3) (1-5) and (t)BuC5(Bn)(SiMe(2))(H)(2) (6) ligands, respectively. The (1)H NMR spectra of the (t)BuC5(SiRR')(H)(3) (1-5) ligands show three pairs of doublets and three singlets for the (t)Bu peaks, consistent with a C(s) symmetry. In the case of the (t)BuC5(Bn)(SiMe(2))(H)(2) (6) ligand, the presence of the monobenzyl group changes the (1)H NMR patterns to indicate a C(1) symmetry. Treatment of (t)BuC5(SiRR')(H)(3) (1-5) or (t)BuC5(Bn)(SiMe(2))(H)(2) (6) with 1 equiv of M(O(t)Bu)(3) (M = Bi, Sb) or Sb(NMe(2))(2) readily yields metalated products of the type [M{(t)BuC5(SiRR')}] (7-16) and [MX{(t)BuC5(Bn)(SiMe(2))}] (X = O(t)Bu, (NMe(2))(2)) (17-19), respectively. All monometallic complexes [M{(t)BuC5(SiRR')}] (7-19) display excellent solubility in organic solvents including pentane and hexane. The (1)H NMR patterns for complexes 7-16 are consistent with a 1,2- or 1,3-alternate conformation while complexes [MX{(t)BuC5(Bn)(SiMe(2))}] (17-19) display patterns for a C(1) symmetry. All crystals show monomeric structures. Ligand (t)BuC5(SiPh(2))(H)(3) (3) displays a distorted cone conformation while the presence of the monobenzyl ether in (t)BuC5(Bn)(SiMe(2))(H)(2) (6) forces a partial cone conformation. Complexes 7-19 all display a distorted 1,2-alternate conformation with the metal centers displaying coordination numbers of three, four or five. No Si...M interactions were observed.

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“…The reaction of BCl 3 with tert-butylcalix [4]areneH 4 produces the chloro-substituted bis(bora)calix [4] arene, which has been reacted with one and two equivalents of 2,4,6-(CF 3 ) 3 C 6 H 2 Li to form the mono-and bis-substituted boracalixarenes respectively. 156 The selective iridium catalysed borylation of the polycyclic aromatics, naphthalene, pyrene and perylene, by B 2 (pin) 2 (pin ¼ OCMe 2 CMe 2 O) has been reported and the molecular structures of the naphthalene-2,7-bis(pinicolboronate) and pyrene-2,7bis(pinicolboronate) and perylene-2,5,8,11-tetra(pinicolborate) esters determined. 157 The same iridium catalyst [Ir(COD)OMe] 2 , has also been used for the regioselective borylation of porphyrins.…”

Section: Boron-chalcogen Compoundsmentioning

confidence: 99%

Boron

Johnson

2006

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Synthesis of bis(bora)calix[4]arenes bearing perfluoroaryl substituents

Abstract: New routes to perfluoroaryl complexes of bis(bora)calix[4]arenes are described; crystallographic and spectroscopic data are presented.

Cited by 8 publications

References 10 publications

Synthesis, X-ray structures and reactivity of calix[5]arene bismuth(iii) and antimony(iii) complexes

Synthesis, X-ray structures and reactivity of calix[5]arene bismuth(iii) and antimony(iii) complexes

Facile Synthesis of Bismuth(III) and Antimony(III) Complexes Supported by Silylated Calix[5]arenes.

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