The reactions of lithium trimethysilylmethyls with isocyanides; structures and reactions of the derived lithium 1-azaallyls, β-diketiminates and a 1-azabuta-1,3-dienyl-3-amide

Hitchcock, Peter B.; Läppert, Michael F.; Layh, Marcus

doi:10.1039/b103553n

Cited by 30 publications

(19 citation statements)

References 23 publications

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“…7 For example, the N-Li average distance is 1.39(1) Å in 4a, compared with 1.98(1) Å in 4aÁ(THF) 2 , akin to the Li-N bond length in related lithium diketiminato 13,14,25,26 and porphyrin complexes. 11 Furthermore, the acute C4-N1-Li and C6-N2-Li bond angles in 4a are only 95.3(4)8 and 96.4(4)8, respectively.…”

Section: Resultsmentioning

confidence: 97%

“…8 Porphyrins, which can be formed from the condensation of two appropriately substituted dipyrrins, undergo deprotonation to give the di-ionic tetradentate ligand, and alkali metalloporphyrins have been well-documented, 9 as has the synthetic utility of such complexes in transmetallation reactions to obtain Ag(I), Zn(II), Cd(II), Hg(II), Cu(II), Sn(II), and Fe(III) complexes of porphyrins. 10 As lithium, sodium, and potassium complexes of porphyrins have all been reported, 11 we found it surprising that alkali complexes of the dipyrrinato ligand were unknown before our work, apart from a single example of a lithium-cryptand-dipyrrinato complex in solution: 12 such derivatives of related b-diketiminato (NacNac), 13,14 porphodimethene, 15 pyrroloimine, 16,17 and amino-pyrrole 18,19 skeletons are well-known.…”

Section: Introductionmentioning

confidence: 89%

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The first series of alkali dipyrrinato complexes

et al. 2010

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The first series of alkali dipyrrinato complexes is reported, encompassing lithium, sodium, and potassium salts of meso-unsubstituted and meso-aryl-substituted derivatives. By varying the substituents at the meso position, the intermolecular distance between the two nitrogen atoms and thus the k 2 -N,N-bidentate bite angle was altered, as confirmed by comparison of crystallographic structures of dipyrrin free-bases in the solid-state. The mode of bonding varies as the ionic radius of the metal ion increases: solid-state structures reveal lithium to be accommodated in the plane of the dipyrrinato unit, whilst sodium is accommodated out of plane. The reactivity of analogous lithium, sodium, and potassium dipyrrinato complexes increases as the ionic radius of the metal ion increases, in keeping with the concept that the complexes tend towards an increasingly ionic nature as the size of the alkali metal increases.Résumé : On rapporte la préparation de la première série de complexes dipyrrinato alcalins comportant les sels de lithium, de sodium et de potassium de dérivés méso non substitués et méso substitués par des groupes aryles. En faisant varier la nature des substituants en position méso, on modifie la distance intermoléculaire entre les deux atomes d'azote et, en conséquence, l'angle de morsure k 2 -N,N du bidentate, tel que confirmé par une comparaison des structures cristallographiques des bases libres dipyrrines à l'état solide. Le mode de liaison varie avec une augmentation du rayon ionique de l'ion métallique; les structures à l'état solide révèlent que le lithium s'accommode dans le plan de l'unité dipyrrinato alors que le sodium est accommodé hors du plan. La réactivité des complexes analogues du lithium, du sodium et du potassium augmente avec une augmentation du rayon ionique du métal ionique, en accord avec le concept que les complexes tendent vers une nature de plus en plus ionique avec une augmentation de la taille des métaux alcalins.

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 89%

The first series of alkali dipyrrinato complexes

et al. 2010

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“…The Li-N bond distances of 1.935 (7) and 1.913 (7) A indicate it to be an amidic structure. The structural character of the Li-N bond is similar to that in the analogue complexes Li{N(Ar)C(R)C[N(Ar)]@ C(H)Ph}(TMEN) [5], {1,3-[2,6-i Pr 2 C 6 H 3 NC(@CH 2 )] 2 -C 6 H 4 }Li 2 (DME) [6], and [{2,6-(SiMe 3 )NC(Bu t )CH} 2 -C 5 H 3 N][Li 2 (THF) 2 ] [7].…”

mentioning

confidence: 65%

“…(7), Li(1)-C(4) 2.360(8), Li(2)-N(2) 1.913 (7), Li(2)-O(3) 1.969 (7), Li(2)-O(4) 1.933(8), N(1)-C(2) 1.346(4), C(1)-C(2) 1.369 (5), N(2)-C(3) 1.354(4), C(3)-C(4) 1.356 (5).…”

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confidence: 98%

Synthesis, characterization of the dilithium bis-azaallyl complex [CH 2 C(NAr)C(NAr) CH 2 ]Li 2 (THF) 4 and its catalytic activity for the anionic polymerization of methyl methacrylate

Long

Yao²,

Shen

2004

Inorganic Chemistry Communications

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“…We are currently interested in the reactions of -H-free isocyanides with trimethylsilyl-substituted lithium amides, alkyls and silyls that have previously led to a wide variety of products. A neutral isocyanide adduct (Caro et al, 1998), a lithium-1-azabuta-1,3-dienylamide (Hitchcock et al, 2001), a silacyclobutene derivative (Hitchcock et al, 1999), and a series of lithium-1-azaallyls (Hitchcock et al, 2001) and lithium-diketiminates (Hitchcock et al, 2001) have so far been isolated and crystallographically characterized. The isolated products are believed to depend on, amongst other factors, the lithium starting material, the solvent, and the steric and electronic properties of the isocyanide.…”

Section: Commentmentioning

confidence: 99%