Reactions of 2-arsa- and 2-stiba-1,3-dionato lithium complexes with group 4–7 metal halides

Jones, Cameron; Williams, Thomas

doi:10.1016/j.jorganchem.2004.02.020

Cited by 11 publications

(6 citation statements)

References 29 publications

(19 reference statements)

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“…As expected, the Li–O term (DME) bonds (1.9621(18) Å) are somewhat shorter than the Li−μ 2 -O(DME) bonds (2.0433(18)–2.2772(18) Å). All Li–O, Li–N, and Li–S distances are in agreement with the analogous distances in other lithium complexes. − Atoms of the Li(1)O(2)Li(1A)O(2A) fragment form a planar ring. The mbt F ligand plane forms an angle equal to 59.57° with the Li 2 O 2 ring.…”

Section: Resultssupporting

confidence: 77%

“…The mbt F ligand plane forms an angle equal to 59.57° with the Li 2 O 2 ring. The Li···Li distance in the complex is 3.161(3) Å, which is characteristic for lithium dimers with bridging DME ligands. , In contrast to complexes 1 and 2 , in a molecule of 3 the four-membered LiNCS metallacycle is almost flat. The dihedral angle between the NLiS and NCS planes is 1.82°.…”

Section: Resultsmentioning

confidence: 95%

“…As expected, the Li− O term (DME) bonds (1.9621(18) Å) are somewhat shorter than ligands. 49,50 In contrast to complexes 1 and 2, in a molecule of 3 the four-membered LiNCS metallacycle is almost flat. The dihedral angle between the NLiS and NCS planes is 1.82°.…”

Section: ■ Introductionmentioning

confidence: 94%

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Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

et al. 2020

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In the search for new f–d luminescent complexes of Eu(II) and Yb(II) the metathesis reactions of diiodides of these metals with perfluorinated 2-mercaptobenzothiazolates of alkali metals were studied. It has been found that the reactions of LnI2(THF)2 (Ln = Eu, Yb) with K(mbtF) (mbtF = perfluorinated 2-mercaptobenzothiazolate anion) in DME result in the formation of the nonluminescent complexes Ln(mbtF)2(DME)2 and precipitation of KI in high yields. Single-crystal X-ray diffraction analyses have shown that Eu(mbtF)2(DME)2 has a trans orientation of mbtF ligands, while in the Yb(mbtF)2(DME)2 molecule the ligands occupy cis positions. The DFT calculations and estimations with the invariom model revealed that the complexes have a flexible coordination sphere of Ln2+ ions and a relatively low energy of Ln–mbtF binding. The reactions of the same diiodides with the lithium complex Li(mbtF) are reversible and proceed through the formation of intermediate complexes of unknown structure which have been isolated as noncrystalline solids. The europium product (solid and in DME solution) upon UV excitation exhibited bright luminescence with λ 510 nm. Data from time-resolved photoluminescence (PL) spectroscopy indicated the existence in the intermediate substance of two Eu2+ emission centers with different coordinating environments. Treatment of the solid intermediate product with toluene led to its dissociation onto Ln(mbtF)2(DME)2 and [LiI(DME)] n . The back-replacement of toluene with DME gives again the solutions from which the starting LnI2 and Li(mbtF)(DME) were precipitated by slow evaporation of the solvent. The reversibility of the processes has been confirmed by the reaction of nonluminescent Eu(mbtF)2(DME)2 with LiI in DME medium, which resulted in the same luminescent solution which gave a mixture of EuI2(DME)3 and Li(mbtF).

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Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 95%

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Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

et al. 2020

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“…For the same reasons, the arsonium centers in 3 (Ph) and in 9 (Me) are also substantially distorted from a tetrahedral geometry. The eclipsed conformation of the diarsonium cation 6 reveals an As−As bond length [2.4109(3) Å] that is only slightly shorter than that in a neutral diarsine ([MesC(O)] 2 As−As[C(O)Mes] 2 = 2.4300(8) Å) . For comparison, a larger difference is observed between the Sb−Sb bond length in the hexamethyldistibonium dication [2.7624(11) and 2.7867(12) Å] and in tetramethyldistibine [2.862(2), 2.830(1), and 2.838(1) Å] …”

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confidence: 99%

Phosphinoarsonium and Diarsonium Cations from Chloride-Abstraction-Induced Pnictogen Coupling

et al. 2008

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“…Dimerization results in a planar four-membered (LiÀ O) 2 ring, a motif common in organolithium chemistry. [6,79,[95][96][97][98] Here, dimerization gives rise to a fused, tricyclic 6-4-6 ring system. The backbone of the NacNac-derived NCCCO unit remains highly delocalised, as evidenced by the lack of a H-atom at the γ-C position and the bond lengths observed, (N1À C1, 1.295(3) Å; C1À C3, 1.473(3) Å; It is proposed that compound 3 is the product of two distinct reactions (see Scheme 4).…”

Section: Isolation and Crystallographic Characterisation Of Organolit...mentioning

confidence: 99%

Crystallographic Characterisation of Organolithium and Organomagnesium Intermediates in Reactions of Aldehydes and Ketones

Mulvey

Lynch

Kennedy

et al. 2022

Helvetica Chimica Acta

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We report reactions of LiNacNac and NacNacMg(TMP) with common organic substrates (TMP=2,2,6,6‐tetramethylpiperidide). Using bulky β‐diketiminate compound NacNac (Me, Dipp), we have trapped metalated intermediates amenable to X‐ray crystallographic study. LiNacNac and acetone produced the NacNac‐free hexameric diacetone alkoxide [{LiO(MeC(=O)CH2C(Me)2}6]; whereas pinacolone gave the simple monomeric donor–acceptor complex [Li{(MeCN‐2,6‐iPr2C6H3)2CH}{O=C(Me)tBu}]. Benzaldehyde produced dimeric [Li{(MeCN‐2,6‐iPr2C6H3)2CC(=O)Ph}{O=C(Ph)OCH2Ph}]2, where one benzaldehyde molecule has inserted in to the γ‐carbon position of the NacNac ligand, with a molecule of benzyl benzoate derived from a Tishchenko reaction of the aldehyde acting as a terminal donor to lithium. Tetranuclear, mixed dimer [{LiO(MeCN‐2,6‐iPr2C6H3)2CH‐CH(Ph)}2{LiO(PhC(=O)}2] containing the same modified NacNac ligand was the fortuitous product from repeating the reaction of LiNacNac and benzaldehyde in a solution presumably contaminated with benzoic acid. Combining NacNacMg(TMP) with pinacolone affords monomeric heteroleptic [Mg{(MeCN‐2,6‐iPr2C6H3)2CH}{OC(tBu)(Me)CH2C(=O)tBu}] with an aldolate constituting the second anion. Completing the set is dimeric [Mg{(MeCN‐2,6‐iPr2C6H3)2CH}{O(C=CH2)Ph}2], where the enolate derived from acetophenone bridges the magnesium centres.

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Reactions of 2-arsa- and 2-stiba-1,3-dionato lithium complexes with group 4–7 metal halides

Cited by 11 publications

References 29 publications

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

Phosphinoarsonium and Diarsonium Cations from Chloride-Abstraction-Induced Pnictogen Coupling

Crystallographic Characterisation of Organolithium and Organomagnesium Intermediates in Reactions of Aldehydes and Ketones

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