Novel octameric structure of the lithium primary amide [{ButN(H)Li}8] and its implication for the directed synthesis of heterometallic imide cages

Barnett, Nicholas D. R.; Clegg, William; Horsburgh, Lynne; Lindsay, David M.; Liu, Qiyong; Mackenzie, Fiona; Mulvey, Robert E.; Williard, P. G.

doi:10.1039/cc9960002321

Cited by 42 publications

(38 citation statements)

References 11 publications

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“…As a consequence, where the cisoid subunits fuse (along the edge bonds, Na1 ± N4' and Na3 ± N1'), the conformation of the amido substituents changes to a transoid setup. This contrasts with the situation found in the lithium analogue 9, [10] where the lack of solvent ligands leads to an exclusively cisoid conformation; this results in a closed cyclic structure comprising eight N ± Li rungs.…”

Section: Introductioncontrasting

confidence: 59%

“…Also reported is the heterobimetallic derivative 8, another curved ladder species, but a finite oligomer with a different combination of cisoid/ transoid units to that found in 7. Furthermore, adding these two new crystal structures to that previously described for 9 [10] not only completes the series of lithium, sodium, and mixed lithium ± sodium structures of tert-butylamide, but it also establishes an unprecedented family of ladder compounds, each of which displays a unique rung size and architecture.…”

Section: Introductionmentioning

confidence: 91%

“…Significantly, the cisoid arrangement of the tBu/H substituents in the all-lithium cyclic ladder 9 [10] is maintained in the central (NLi) 2 section of the mixed lithium ± sodium open ladder structure 8 ( Figure 3). A switch to a transoid conformation occurs within its outer (NLiNNa) rings.…”

Section: Introductionmentioning

confidence: 98%

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New Alkali Metal Primary Amide Ladder Structures Derived fromtBuNH2: Building Cisoid and Transoid Ring Conformations into Ladder Frameworks

et al. 1998

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Two novel alkali metal amide ladder complexes have been synthesised and crystallographically characterised. Derived from the same primary amine precursor (tBuNH 2 ), they represent important additions to the series of ladder arrangements previously established within secondary amide chemistry. Thus the sodium amide´amine complex [{[tBuN(H)Na] 3´H2 NtBu} I ] forms an infinite wavelike ladder structure. Covering three nitrogen ± sodium rungs, its curved sections display a cisoid conformation of amide substituents; but where these curved sections fuse, a transoid conformation is found. Every third sodium cation along the ladder framework is ligated by a tert-butylamine solvent molecule. In contrast, the heterobimetallic derivative, [{[tBuN(H)] 2 LiNat meda} 2 ], adopts a finite oligomeric ladder structure limited to only four nitrogen ± metal rungs in length. The central rungs contain lithium, while the outer rungs contain sodium. As in the all-sodium structure, the ladder is curved; there is a mixture of cisoid and transoid ring conformations within its framework. TMEDA solvent molecules complete the structure by chelating the sodium cations at the ladder ends.

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Section: Introductioncontrasting

confidence: 59%

Section: Introductionmentioning

confidence: 91%

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New Alkali Metal Primary Amide Ladder Structures Derived fromtBuNH2: Building Cisoid and Transoid Ring Conformations into Ladder Frameworks

et al. 1998

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“…As reported elsewhere, lithium salts of primary amines are highly reactive and unstable if not stabilized by a base such as N,N,NЈ,NЈ-tetramethylethylenediamine. [18][19][20] Only the hexameric salt (tBuNHLi) 6 has been reported to be stable without any coordinating base. [18] Therefore, the in situ preparation of a known amount of the amine salt was accomplished by slow addition of an excess amount of the corresponding amine to a solution of a known amount of MeLi or nBuLi in THF at -78°C.…”

Section: Resultsmentioning

confidence: 99%

“…[18][19][20] Only the hexameric salt (tBuNHLi) 6 has been reported to be stable without any coordinating base. [18] Therefore, the in situ preparation of a known amount of the amine salt was accomplished by slow addition of an excess amount of the corresponding amine to a solution of a known amount of MeLi or nBuLi in THF at -78°C. The resulting suspension was warmed to ambient temperature and after stirring for 30 min added dropwise to a solution of LGaCl 2 at -78°C.…”

Section: Resultsmentioning

confidence: 99%

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

et al. 2009

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The facile preparation of β-diketiminate gallium amides with general formulas of either LGa(NHR) 2 {L = [HC{C(Me)N-(Ar)} 2 ]-, Ar = 2,6-iPr 2 C 6 H 3 ; R = Et (1), iPr (2), nBu (3), Ph (4)} or LGa(NHR)Cl [R = tBu (5); Et (6)] was accomplished by the reaction of LGaCl 2 with the lithium salt of the corresponding amine in 1:2 (1-4) or 1:1 (5, 6) molar ratios. Compounds 1-6 are useful synthons for further synthesis, as the amide substituents are excellent leaving groups, and the resulting amines can be cleanly and easily removed from the reaction matrix. To demonstrate this, compounds 1 and 5 were treated with ethanol, leading to the alcoholysis products LGa(OEt) 2

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et al. 2004

Inorganic Syntheses

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Diborane(4) compounds are key reagents in transition-metal-catalyzed diboration 1 and Suzuki-Miyaura coupling reactions. 2 Two of the most widely used compounds are the pinacolate derivative B 2 (pin) 2 (pin ¼ OCMe 2 CMe 2 O) 3 and the catecholate species B 2 (cat) 2 (cat ¼ 1,2-O 2 C 6 H 4 ), 4 both of which are prepared from tetrakis(dimethylamino) diborane(4), B 2 (NMe 2 ) 4 , described initially by Brotherton. 5 Detailed preparations for B 2 (pin) 2 and B 2 (NMe 2 ) 4 have been described in Ref. 3b. Here we present a slightly different preparation for B 2 (NMe 2 ) 4 together with details of the synthesis of 1,2-B 2 Cl 2 (NMe 2 ) 2 6 and B 2 (cat) 2 . Simple modifications of the B 2 (cat) 2 synthesis given here allow for the preparation of a host of diol-derived diborane(4) compounds.All solvents were freshly distilled under dinitrogen from an appropriate drying agent immediately prior to use. Glassware was either kept in an oven at 150 C overnight or flame-dried under vacuum. All manipulations were carried out under dinitrogen using standard Schlenk techniques. Procedure& Caution. Sodium can spontaneously ignite on exposure to water or air. BCl 3 fumes vigorously in air, producing HCl. These reagents should only be handled in a fume hood.To a two-necked 250-mL round-bottomed flask equipped with a sidearm and a magnetic stirring bar and mounted on a magnetic stirrer, B(NMe 2 ) 3 (Aldrich, 33 mL, 0.2 mol) is added under a constant stream of nitrogen and stirring is started. The flask is then cooled to about À78 C by means of an external dryice ethanol bath, and a solution of BCl 3 in heptane (Aldrich, 100 mL of a 1.0 M solution) is added. (Note: It is important that heptane rather than hexane be used, since yields are much lower when hexane is employed.) The reaction mixture is then stirred at low temperature for 1 h, after which time the cooling bath is removed, and the reaction flask and contents are allowed to warm to room temperature. Stirring is continued for a further 3 h. After this time the reaction mixture forms a pale yellow solution with small quantities of a white solid.[Note: Checkers state that at this stage the reaction can be assayed by 11 B NMR, although this is rarely necessary if freshly distilled or purchased BCl 3 and B(NMe 2 ) 3 are used. The solid can be removed by filtration, although its presence in subsequent steps seems not to affect the yield.] Clean metallic sodium (6.9 g, 0.3 mol) is then slowly added in small pieces, and afterward a Liebig condenser is attached to the reaction flask. The magnetic stirrer is replaced with a stirrer-heating mantle, and the reaction mixture is then refluxed for 16 h, resulting in a brown solution and a purple precipitate. After cooling to room temperature, the condenser is removed, and the reaction mixture is then filtered through a glass frit into a separate flask. The filter cake is washed with hexanes (2 Â 10 mL). All solvent is removed from the filtered reaction solution by vacuum pumping (standard vacuum pump) at room temperature, affording a bro...

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Novel octameric structure of the lithium primary amide [{ButN(H)Li}8] and its implication for the directed synthesis of heterometallic imide cages

Cited by 42 publications

References 11 publications

New Alkali Metal Primary Amide Ladder Structures Derived fromtBuNH2: Building Cisoid and Transoid Ring Conformations into Ladder Frameworks

New Alkali Metal Primary Amide Ladder Structures Derived fromtBuNH2: Building Cisoid and Transoid Ring Conformations into Ladder Frameworks

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

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