2 ? 1 Ba/Ti(iv) Heterobimetallic complex based on two calix[6]arenes

Petrella, Antonella J.; Roberts, Nicholas K.; Craig, Donald C.; Raston, Colin L.; Lamb, Robert N.

doi:10.1039/b302346j

Cited by 13 publications

(10 citation statements)

References 17 publications

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“…In complex 4a the three antimony atoms are linked by two bridging oxygens [O (7) and O(8)] that do not belong to the calixarene ligand. Similarly, we have observed bridging oxygens appearing in calix [5]arene 22 and even-numbered calixarene complexes 20,21 of both bismuth and antimony. Bismuth complexes 6, 7, and 8 (vide infra) will also feature bridging oxygens of an unknown source.…”

Section: Synthesis and Characterizationsupporting

confidence: 76%

“…2 and 3, respectively, and selected bond distances and angles are listed in Table 1. Complexes 1 and 2 display very similar features and are structurally analogous to our calix [5]arene complex [Bi{ t BuC5(H) 2 }]. 22 Both complexes exhibit a dimeric structure with a bismuth atom coordinated to each calixarene lower rim, and contain an inversion center located halfway between the two bismuth atoms.…”

Section: Synthesis and Characterizationmentioning

confidence: 67%

“…23,24 This is the second part of our studies involving the synthesis of bismuth(III) and antimony(III) complexes with large calix[n]arenes (n = 5-8). The first part is a companion article in which we describe the preparation and reactivity of calix [5]arene Bi(III) and Sb(III) complexes. 22 Herein we describe the synthesis and full characterization of a series of bismuth and antimony calix[n]arene (n = 6-8) complexes.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

2009

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A series of calix[n]arene (n=6-8) bismuth and antimony complexes were synthesized and fully characterized by NMR, X-ray, IR, UV-Vis and elemental analysis. The monobismuth calix[6]arene complex [Bi{tBuC6(H)3}]2 1 was prepared by the reaction of para-tert-butylcalix[6]arene (tBuC6(H)6) with one equivalent of Bi[N(SiMe3)2]3. Complex 1 featured a Bi2(micro-O)2 central core similar to other bismuth calixarene complexes prepared by our group. Reaction of calix[6]arene (HC6(H)6) with two equivalents of Bi(OtBu)3 yielded different outcomes depending on the reaction solvent. If THF was used, complex [Bi{HC6(H)3}] 2 was obtained in 72% yield; however, when toluene was used, complexes 2 and [Bi2{HC6}] 3 were isolated in 23 and 57% yields, respectively. Mononuclear complexes 1 and 2 displayed dimeric structures in the solid state with cone-like conformations for the calixarene ligands. The 1H NMR spectrum of complex 2 displays patterns for an asymmetric structure with two signals in a 2:1 ratio for the unreacted OH groups. Treatment of calix[6]arenes RC6(H)6 (R=H, tBu) with two equivalents of SbR3 (R=OtBu, NMe2) produced dinuclear complexes [Sb2{HC6}] 4, and [Sb2{tBuC6}] 5, respectively. The 1H NMR spectra for the dinuclear complexes 3, 4, and 5 showed the characteristic calixarene pattern for a 1,2,3-alternate conformer. In the process of recrystallization of complex 4 an unexpected trimetallic complex with composition [Sb3O2{HC6(H)}] 4a was obtained in low yield. Treatment of para-tert-butylcalix[7]arene (tBuC7(H)7) with two equivalents of Bi(OtBu)3 produced the bimetallic complex [Bi2O{tBuC7(H)3}]2 6. Complex 6 contains an overall Bi4O2(OAr)8 core system with a structural resemblance to other bimetallic bismuth calixarene complexes reported by our group. The larger para-benzylcalix[8]arene (BnC8(H)8) and calix[8]arene (HC8(H)8) reacted with excess Bi(OtBu)3 to produce the tetranuclear complexes [Bi4O2{HC8}] 7 and [Bi4O2{BnC8}] 8, respectively. The solid state structure of complex 8 featured a dimeric unit with the calixarene ligands in pinched-cone conformation and displaying an overall Bi8O4(OAr)16.H2O core. No metal pi-arene interactions were observed.

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Section: Synthesis and Characterizationsupporting

confidence: 76%

Section: Synthesis and Characterizationmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

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Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

2009

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“…In contrast, for mixed 2:1 Ba-(Ti/Zr(IV)) calix [6]arene complexes, Fig. 10, the coordination of either titanium or zirconium appears to stabilise the endo-complexation of barium by fixing the calix [6]arene in the 1,3 alternate conformation [29,30]. While attempts to make mono-barium calix[6]-arene complexes have been unsuccessful, an interesting complementarity of coordination modes is displayed in the multi-metallic barium calix [6]arene complex, Fig.…”

Section: Calix[6]arenesmentioning

confidence: 61%

Calixarenes as platforms for the construction of multimetallic complexes

Petrella

Raston

2004

Journal of Organometallic Chemistry

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“…10 In this context, Cs ϩ and Ba 2ϩ have had a remarkable influence on the reactivity of p-tert-butylcalix [6]arene towards the uranyl ion 11 and titanium, respectively. 12 Potassium similarly activates calix [5]arene towards reaction with titanium. 13 Another consideration in devising synthetic strategies for preparing transition metal calixarene complexes is the possible formation of binuclear, and higher oligomeric complexes.…”

Section: Introductionmentioning

confidence: 99%

A facile route to hetero-bimetallic Ti(iv)-alkali metal calix[4]arene complexes

et al. 2003

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Deprotonation of calix [4]arenes by alkali metal in methanol using simple benchtop procedures is effective in the formation of novel monomeric and dimeric titanium() complexes. For the larger alkali metal cations, K ϩ and Cs ϩ , favourable complexation within the π-basic calix[4]arene cavity facilitates the formation of monomeric titanium() complexes when oligomer formation is inhibited by an acetylacetonate ligand. In contrast, the smaller Li ϩ and Na ϩ ions preferentially form dimeric complexes with exo-bridging alkali and titanium() metal centres. A dimeric complex is also obtained for potassium in the absence of acetylacetonate. The solid state structures of the K-Ti and Na-Ti calix[4]arene dimer complexes show different structural characteristics depending on the nature of the alkali metal.

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2 ? 1 Ba/Ti(iv) Heterobimetallic complex based on two calix[6]arenes

Abstract: Reaction of p-Bu(t)-calix[6]arene with barium metal in methanol then [Ti(OPr(i))4] affords a heterobimetallic complex with a central Ti(IV) attached to two calix[6]arenes in the 1,3-alternate conformation, each with an endo-barium sharing common phenolate groups with the titanium centre.

Cited by 13 publications

References 17 publications

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Calixarenes as platforms for the construction of multimetallic complexes

A facile route to hetero-bimetallic Ti(iv)-alkali metal calix[4]arene complexes

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