Synthetic and reactivity studies of hetero-tri-anionic sodium zincates

Francos, Javier; Kennedy, Alan R.; O’Hara, Charles T.

doi:10.1039/c5dt04329h

Cited by 6 publications

(4 citation statements)

References 84 publications

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“…The Na−N TMP distance of 2.379(3) Å is, as expected, slightly shorter than the Na−N TMEDA bond distances (2.482(4) and 2.471(4) Å). This structural motif is similar to those reported for related bis(alkyl) sodium TMP‐zincates [8] . If we compare the Na−N TMP distance with other related complexes, (TMEDA)NaZn(TMP) t Bu 2 (Na−N TMP : 2.432(2) Å), [36] or (TMEDA⋅NaTMP) 2 (Na−N TMP : 2.4273(18) and 2.5420(17) Å), [37] a slightly shorter Na−N TMP distance is observed in 1 , likely due to the presence of less bulky ethyl groups at the zinc centre.…”

Section: Discussionsupporting

confidence: 86%

“…This structural motif is similar to those reported for related bis(alkyl) sodium TMP-zincates. [8] If we compare the NaÀ N TMP distance with other related complexes, (TMEDA)NaZn(TMP) t Bu 2 (NaÀ N TMP : 2.432(2) Å), [36] or (TMEDA•NaTMP) 2 (NaÀ N TMP : 2.4273(18) and 2.5420(17) Å), [37] a slightly shorter NaÀ N TMP distance is observed in 1, likely due to the presence of less bulky ethyl groups at the zinc centre. Compound 1 was also characterised in C 6 D 6 solution by 1 H-and 13 C-NMR.…”

Section: Discussionmentioning

confidence: 99%

“…With a growing emphasis on sustainability in organometallic chemistry and the superior reactivity expected for this type of reagents, the interest in the synthesis and reactivity of organosodium compounds has significantly increased in the recent years [5] . Within the area of deprotonative metalation, several studies have disclosed the enormous potential of sodium amides, [6] as well as bimetallic systems which combine Na with a another divalent metal such sodium zincates, [7–9] magnesiates, [10–12] and ferrates [13–15] . Sodium alkyls can also engage in other cornerstone reactions such as Na‐halogen exchange, [16] or palladium‐catalysed cross‐couplings [17,18] .…”

Section: Introductionmentioning

confidence: 99%

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Gram‐Scale Synthesis, Isolation and Characterisation of Sodium Organometallics:nBuNa and NaTMP

Tortajada

Anderson

Hevia

2022

Helvetica Chimica Acta

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Organolithium compounds represent one of the most widely utilised commodity reagents in synthetic chemistry. However, their analogues with the heavier alkali-metal sodium are much less utilised and their reactivity is less understood. Recent studies have shown the excellent potential of organosodium reagents in synthesis, finding widespread applications in cornerstone organic transformations such as deprotonative metalation, metal-halogen exchange or Pd catalysed CÀ C bond formation. However, detailed procedures for the preparation of these compounds are scarce. Therefore, we report a step-by-step synthesis of two organosodium reagents: nBuNa and NaTMP (TMP = 2,2,6,6-tetramethylpiperidide) as key building blocks in sodium organometallics, which allows the easy access to other sodiated compounds and enables chemical reactivity that is not feasible with organolithium compounds. Both can be prepared in high yields (up to 92 %), and isolated as pure solids that can be stored under argon for long periods of time (up to six months) without observed degradation.Here we further illustrate the synthetic utility of NaTMP as an efficient metalating reagent for 1-methoxynaphthalene which can be subsequently employed in Suzuki -Miyaura couplings, as well as a precursor for sodium zincate [(TMEDA)NaZn(TMP)Et 2 ], which has been obtained by co-complexation of NaTMP, ZnEt 2 and TMEDA in hexane, for which a structure has been established by X-ray crystallography.

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Section: Discussionsupporting

confidence: 86%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Gram‐Scale Synthesis, Isolation and Characterisation of Sodium Organometallics:nBuNa and NaTMP

Tortajada

Anderson

Hevia

2022

Helvetica Chimica Acta

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“…A black and white example of a bimetallic synergistic effect is evidenced in the formation of the mixed alkyl sodium zincate [(TMEDA)Na(TMP)( n Bu)Zn( t Bu)] ( 138 ) from an equimolar mixture of n -butylsodium, di- tert -butylzinc, TMP(H), and TMEDA (Scheme ). It may have been anticipated that the strong base n -butylsodium would have deprotonated TMP(H) to generate the amide NaTMP and butane, and that the weak base di- tert -butylzinc would then simply cocomplex with NaTMP in the presence of TMEDA to produce the sodium homoalkylzincate 123 . Instead it appears that a synergistic intermediate [(TMEDA)Na( n Bu)( t Bu)Zn( t Bu)] ( 139 ) is formed and that this reacts with TMP(H) through its most basic alkyl t Bu ligand (Scheme ).…”

Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

2019

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The development of synthetic chemistry since the early 1900s owes much to the service of organolithium reagents. Brilliant bases (e.g., deprotonating C−H bonds), nucleophiles (e.g., adding to unsaturated molecules), and transfer agents (e.g., delivering ligands to other metals), these versatile virtuosi and to a lesser extent the organic derivatives of the other common alkali metals sodium and potassium have proved indispensable in both academia and technology. Today these monometallic compounds are still utilized widely in synthetic campaigns, but in recent years they have been joined by an assortment of bimetallic formulations that also contain an alkali metal but in company with another metal. These bimetallic formulations often exhibit unique chemistry that can be interpreted in terms of synergistic effects, for which the alkali metal is essential, though it is often the second metal that performs the synthetic transformation. Here, this "alkali-metal-mediated" chemistry is surveyed focusing mainly on bimetallic formulations containing two alkali metals or an alkali metal paired with magnesium, calcium, zinc, aluminum, or gallium. In this International Year of the Periodic Table (IYPT), we ponder whether a Pairiodic Table of Element Pairs will emerge in the future.

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Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

2016

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Sterically encumbered 4‐hydroxy‐3,5‐diisopropylbenzoic acid (H2diphba), bearing a carboxylic acid, a phenol and two iso‐propyl substituents, has been investigated for the first time as a ligand and supramolecular synthon to isolate eight Zn(II) complexes, [Zn2(Hdiphba)3(OAc)(L)] (L=DMF(1) or pyz (2)), [Zn(Hdiphba)2(2,2′‐bpy)] (3), [Zn(Hdiphba)2(1,10‐phen)] (4), [Zn(Hdiphba)2(pz)2] (5) and [Zn2(Hdiphba)2(μ2‐dmpz)2(Hdmpz)2] (6), [Zn(Hdiphba)2(4,4′‐bpy)]n⋅4nCH3OH (7.4nCH3OH), [Zn2(Hdiphba)4(4,4′‐azobpy)(H2O)2] (8⋅H2diphba), which have been structurally characterized. Compounds 1 and 2 are rare examples of symmetrically bridged triple‐blade molecular tricarboxylate paddle‐wheels which self‐assemble into hexameric units. Compounds 3, 4 and 5 are mononuclear complexes, bearing two exposed phenolic –OH groups self‐assembled into 2‐D arrays via both hydrogen bonding and π‐π stacking interactions. Compound 6 is a rare example of bis‐pyrazolate bridged dinuclear Zn(II) complex with two pyrazole N−H and two phenolic ‐OH groups on the molecular periphery to form hydrogen bonds. The use of 4,4’‐bpy leading to a zig‐zag 1‐D polymer 7 composed of [Zn(Hdiphba)2(4,4’‐bpy)]n chains, positioned 10.77 Å apart. The 1‐D channels of 7 are occupied by hydrogen bonded methanol with a rare (CH3OH)4 cluster as the repeating unit. Compound 8 is a discrete bimetallic complex, isolated with a free H2diphba ligand. The photoluminescence spectra of 1–8 exhibit ligand centered emission at around 325 nm.

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Synthetic and reactivity studies of hetero-tri-anionic sodium zincates

Cited by 6 publications

References 84 publications

Gram‐Scale Synthesis, Isolation and Characterisation of Sodium Organometallics:nBuNa and NaTMP

Gram‐Scale Synthesis, Isolation and Characterisation of Sodium Organometallics:nBuNa and NaTMP

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

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