Synthesis and structural investigations of Ni(II)- and Pd(II)-coordinated α-diimines with chlorinated backbones

Pascu, Sofia I.; Baláȥs, Gábor; Green, Jennifer C.; Green, Malcolm L. H.; Vei, Ino C.; Warren, John E.; Windsor, Caroline

doi:10.1016/j.ica.2009.11.009

Cited by 11 publications

(3 citation statements)

References 51 publications

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“…The discovery of the -diimines led to the preparation of the Brookhart-type Group 10 catalysts, which constituted a paradigm shift in transition metals catalysis in the last decade of the 20 th century [1][2][3][4][5][6][7]. Bis(imidoyl)chloride, a versatile ligand incorporating both diimine and dichloride functionalities can be used as a starting material in the synthesis of diimine [8], heterocyclic [9,10] or oxalamidine [11,12] ligands when reacted with the suitable alkyl group, dianions or amines [13]. The steric and electronic effects of these versatile ligands are known to be programmable through the variations of the substituents on the nitrogen atoms [11] and to the groups attached to the carbon atoms.…”

Section: Introductionmentioning

confidence: 99%

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Chen

Fischer²,

Windsor³

et al. 2016

Polyhedron

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Reaction between lithium indenyl and a chlorine substituted alpha diimine of the form [{Cl(NPh) 2 }C)] 2 unexpectedly yielded the corresponding NH rearranged derivative [PhN(H)C(C 9 H 6)] 2 (1) rather than the predicted-diimine. This compound 1 was characterised by 1 H NMR, 13 C{ 1 H} and mass spectrometry, and additionally by X-ray diffraction. It was found that 1 was the first indene-substituted and symmetric secondary amine which was also highly fluorescent in DMSO. The reactivity of 1 towards simple inorganic and organometallic transition metals precursors based on the MX 2 fragments, where M = Group 10 metals and X = halides or methyl groups, has been investigated. Surprisingly, the reaction with [PtMe 2 (COD)] led to the coupling reaction between the indenyl groups incorporated at the CC ligand backbone and a new ligand (2) was discovered, in an attempt to synthesise the metal-linked diamine. Single crystal X-ray diffraction studies confirm this compound 2 to feature coupled indenyl residues and delocalised CC bonds in the solid state. Structural authentication by X-ray crystallography showed compound 2 to be a very rare example of flat and extended aromatic organic molecule and mass spectrometry, IR and NMR spectroscopy were carried out to gain further insight into the solid state and solution phase structures. Further experiments to synthesise analogues of [PhN(H)C(Ind)] 2 aiming to shift a likely equilibrium in favour the imine tautomer, by introducing bulky ortho substituents onto the benzene ring (R = Me, iPr) showed the presence of the imine tautomer to be increasingly favoured in 1 H NMR spectra, with an increase in the steric bulk of the ortho substituents. However, the enamine tautomer is still observed to a minor extent even with isopropyl substituents and yields of these desired compounds were low on steric grounds.

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Section: Introductionmentioning

confidence: 99%

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Chen

Fischer²,

Windsor³

et al. 2016

Polyhedron

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“…After reaction mixture was left stirring under nitrogen atmosphere for 24 h, DNSCH was isolated and crystallized from ethyl acetate/hexane to afford DNSCH in 81% (the spectroscopic identification for DNSCH is accomplished and can be found in Supplementary Material). The C=N group formed is aimed to provide the chelation to metal ions since it is known that C=N exhibits good degree of affinity towards transition and post-transition metal cations due to its electronic structure [16,17].The selectivity of DNSCH towards metal ions was investigated (Fig. 1).…”

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“…The chelation between DNSCH and Fe 3+ is facilitated by the extra coordination from i) C = N group which is known for the strong binding affinity to transition and post-transition metals [16,17] and ii) the 2-hydroxyl group. These functional groups are in the positions where Fe 3+ is held close enough to the dansyl fluorophore.…”

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Highly selective fluorescent chemosensor for Fe3+ imaging in living cells

Smanmoo¹,

Nasomphan²,

Tangboriboonrat³

2011

Inorganic Chemistry Communications

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Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Fedushkin¹,

Nikipelov²,

Morozov³

et al. 2011

Chemistry A European J

103

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Acetylene, phenylacetylene, and alkylbutynoates add reversibly to (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene) to give addition products [dpp-bian(R(1)C=CR(2))]Ga-Ga[(R(2)C=CR(1))dpp-bian]. The alkyne adds across the Ga-N-C section, which results in new carbon-carbon and carbon-gallium bonds. The adducts were characterized by electron absorption, IR, and (1)H NMR spectroscopy and their molecular structures have been determined by single-crystal X-ray analysis. According to the X-ray data, a change in the coordination number of gallium from three [in (dpp-bian)Ga-Ga(dpp-bian)] to four (in the adducts) results in elongation of the metal-metal bond by approximately 0.13 Å. The adducts undergo a facile alkynes elimination at elevated temperatures. The equilibrium between [dpp-bian(PhC=CH)]Ga-Ga[(HC=CPh)dpp-bian] and [(dpp-bian)Ga-Ga(dpp-bian) + 2 PhC≡CH] in toluene solution was studied by (1)H NMR spectroscopy. The equilibrium constants at various temperatures (298≤T≤323 K) were determined, from which the thermodynamic parameters for the phenylacetylene elimination were calculated (ΔG°=2.4 kJ mol(-1), ΔH°=46.0 kJ mol(-1), ΔS°=146.0 J K(-1) mol(-1)). The reactivity of (dpp-bian)Ga-Ga(dpp-bian) towards alkynes permits use as a catalyst for carbon-nitrogen and carbon-carbon bond-forming reactions. The bisgallium complex was found to be a highly effective catalyst for the hydroamination of phenylacetylene with anilines. For instance, with [(dpp-bian)Ga-Ga(dpp-bian)] (2 mol%) in benzene more than 99% conversion of PhNH(2) and PhC≡CH into PhN=C(Ph)CH(3) was achieved in 16 h at 90 °C. Under similar conditions, the reaction of 1-aminoanthracene with PhC≡CH catalyzed by (dpp-bian)Ga-Ga(dpp-bian) formed a carbon-carbon bond to afford 1-amino-2-(1-phenylvinyl)anthracene in 99% yield.

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Synthesis and structural investigations of Ni(II)- and Pd(II)-coordinated α-diimines with chlorinated backbones

Cited by 11 publications

References 51 publications

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Investigations into the reactivity of lithium indenyl with alpha diimines with chlorinated backbones and formation of related functional ligands and metal complexes

Highly selective fluorescent chemosensor for Fe3+ imaging in living cells

Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

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