Neutral and cationic enantiopure group 13 iminophosphonamide complexes

Goswami, Bhupendra; Yadav, Ravi; Schoo, Christoph; Roesky, Peter W.

doi:10.1039/c9dt04082j

Cited by 11 publications

(7 citation statements)

References 53 publications

(59 reference statements)

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“…As with carbon-supported aluminum hydride systems, a common reactivity pathway is the hydroalumination of organic π-bonds. Given the plethora of new N -donor aluminum hydride systems reported in the past two decades, ,− this section will aim to focus on the new bonding motifs and reactivity pathways uncovered in this area.…”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

“…841 Reactivity-wise, few reports of the chemistry of isolated indium hydride species have been published, although their in situ generation and applications in organic synthesis (e.g., as a radical initiator) have been discussed (see also Section 5.4.3). 875−877 Halide/hydride exchange has been reported for the quinuclidine adduct (quin) 2 InH 3 (693) in the presence of LiBr, initially generating (quin) 2 InH 2 Br (694). Compound 694 subsequently undergoes reductive dehydrogenation and disproportionation to generate the mixed valence penta-indium cluster [In 5 Br 8 (quin) 4 ] − , as the [H(quin) 2 ] + salt (695).…”

Section: And Scheme 1 0 0 ) T H E I N D I U M S Y S T E M [ L I ( T ...mentioning

confidence: 99%

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Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

Section: And Scheme 1 0 0 ) T H E I N D I U M S Y S T E M [ L I ( T ...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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“…Very recently, we have synthesized a chiral version of an iminophosphonamide ligand ( L ‐H) and found that it allows further derivatization into alkali and group 13 metal complexes [5b, 6] . The complexes [M 2 ( L ) 2 ] (M=alkali metals, Figure 1) showed exciting photoluminescence (PL) properties, including bright long‐lived phosphorescence at low temperature and thermally activated delayed fluorescence (TADF) with a high quantum yield at ambient temperature.…”

Section: Introductionmentioning

confidence: 99%

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis

Goswami

Feuerstein

Yadav

et al. 2021

Chemistry A European J

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The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L‐H (L=[Ph2P{N(R)CH(CH3)Ph}2]), L′‐H (L′=[Ph2P{NDipp}{N(R)CH(CH3)Ph}]), (Dipp=2,6‐iPr2C6H3), and L′′‐H (L′′=[Ph2P{N(R)CH(CH3)naph}2]), (naph=naphthyl) is presented. The resulting structures [L2Ca], [L′2Ca], and [L′′2Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [L′′2Ca] is assigned to the fluorescence of naphthyl groups, the PL of [L2Ca] and [L′2Ca] is contributed by long‐lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.

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“…At the same time, the length of the Ga–Cl bond lies in its typical range. The gallium atom in n Bu 8 PcGaCl has a coordination number of 5, which is rare for gallium complexes. − …”

Section: Development Of the Catalytic Strategymentioning

confidence: 99%

Synthesis of the Cationic Gallium Phthalocyanines and Their Catalytic Application in Gallium(III)-Activated Processes for Donor–Acceptor Substrates

et al. 2020

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The novel class of gallium catalysts based on cationic gallium phthalocyanines (RPcGa+) with SbF6 – and Sb2F11 – weakly coordinating anions was developed in order to using in the catalytic version for gallium-specific chemistry. Two cycloaddition/annulation processes of styrylmalonates with aromatic aldehydes and styrene were implemented in the catalytic version using this approach. The synthetic strategy to gallium phthalocyanines and their structural features were studied in details, including the use of specially adapted 71Ga NMR spectroscopy in combination with 19F and 121Sb ones, as well as the mechanistic aspects.

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Neutral and cationic enantiopure group 13 iminophosphonamide complexes

Abstract: Utilising the enantiopure iminophosphonamide ligand the enantiopure group 13 metal complexes have been synthesised. The cationic complexes have been accessed using halide abstraction.

Cited by 11 publications

References 53 publications

Molecular Main Group Metal Hydrides

Molecular Main Group Metal Hydrides

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis

Synthesis of the Cationic Gallium Phthalocyanines and Their Catalytic Application in Gallium(III)-Activated Processes for Donor–Acceptor Substrates

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