The reductive disproportionation of CO2 using a magnesium(i) complex: analogies with low valent f-block chemistry

Lalrempuia, Ralte; Stasch, Andreas; Jones, Cameron

doi:10.1039/c3sc52242c

Cited by 88 publications

(85 citation statements)

References 35 publications

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“…From this aluminium oxide intermediate, the reaction proceeds via assimilation of a second equivalent of the substrate to give the isolated products 2 and 3 . Similar mechanisms have been reported for other low‐oxidation state main group complexes with CO 2 , such as [(Nacnac)Mg] 2 reported by Jones and the acyclic silyene [(NHI)Si−Si(SiMe 3 ) 3 ] (NHI=N‐heterocyclic iminato ligand) reported by Inoue …”

Section: Figuresupporting

confidence: 82%

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

et al. 2019

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Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K2[(NON)Al]2 (NON=4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO2, PhNCO and N2O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [(NON)AlO(THF)]−, which features discrete Al−O bonds and dimerizes in the solid state via weak O⋅⋅⋅K interactions. This species reacts with a range of small molecules including N2O (to give a hyponitrite ([N2O2]2−) complex) and H2, the latter offering an unequivocal example of heterolytic E−H bond cleavage across a main group M−O bond.

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Section: Figuresupporting

confidence: 82%

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

et al. 2019

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“…Similarly, reaction of 1 with the carbodiimide, Pr i NCNPr i , led to a two-electron reduction of the substrate, and its insertion into the Mn−Mg bond of the bimetallic compound, giving a good yield of the high-spin (μ eff = 5.1 μ B ) magnesium manganesio-amidinate complex, L † Mn{κ 1 -C,κ 2 -N,N′−C(NPr i ) 2 }Mg( Mes Nacnac) 6 (see SI for further details). 22 It is of note that this reactivity is broadly similar to that displayed by β-diketiminato magnesium(I) dimers, e.g., ( Dip Nacnac)-MgMg( Dip Nacnac), 13,23 which suggests that 1 may well prove of comparable utility to such compounds as a reducing agent in organic synthesis and small molecule activations.…”

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confidence: 93%

A Two-Coordinate Manganese(0) Complex with an Unsupported Mn–Mg Bond: Allowing Access to Low Coordinate Homo- and Heterobimetallic Compounds

et al. 2014

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This study details the synthesis and characterization of an unprecedented two-coordinate, high-spin manganese(0) complex that incorporates an unsupported Mn-Mg bond, viz. L(†)MnMg((Mes)Nacnac) (L(†) = -N(Ar(†))(SiPr(i)3), Ar(†) = C6H2{C(H)Ph2}2Pr(i)-2,6,4; (Mes)Nacnac = [(MesNCMe)2CH](-); Mes = mesityl). This compound has been utilized as an "inorganic Grignard reagent" in the preparation of the first two-coordinate manganese(I) dimer, L(†)MnMnL* (L* = -N(Ar*)(SiMe3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4), and the related mixed valence, bis(amido)-hetereobimetallic complex, Mn(II)(μ-L(†))(μ-L*)Cr(0). It is also shown to act as a two-electron reducing agent in reactions with unsaturated substrates.

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“…Recent examples include systems featuring reduced Mg–Mg, 42 Cr–Cr, 43 and Pd–Pd cores 44 and a highly polar heterobimetallic Zr–Co complex recently reported by Thomas and co-workers. 45 …”

Section: Introductionmentioning

confidence: 99%

The Reductive Activation of CO₂Across a Ti═Ti Double Bond: Synthetic, Structural, and Mechanistic Studies

2015

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The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti2Pn†2 (1) (Pn† = 1,4-{SiiPr3}2C8H4) with CO2 is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO2 reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO2 molecule bound symmetrically to the two Ti centers in a μ:η2,η2 binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO2 is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η8 fashion to each of the formally TiIII centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti2Pn2 (Pn = C8H6) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO2 reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-TiIII species to yield di-TiII and di-TiIV products. 1 forms a structurally characterized, thermally stable CS2 adduct 8 that shows symmetrical binding to the Ti2 unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph3PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved.

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The reductive disproportionation of CO2 using a magnesium(i) complex: analogies with low valent f-block chemistry

Cited by 88 publications

References 35 publications

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

A Two-Coordinate Manganese(0) Complex with an Unsupported Mn–Mg Bond: Allowing Access to Low Coordinate Homo- and Heterobimetallic Compounds

The Reductive Activation of CO₂Across a Ti═Ti Double Bond: Synthetic, Structural, and Mechanistic Studies

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The reductive disproportionation of CO2 using a magnesium(i) complex: analogies with low valent f-block chemistry

Cited by 88 publications

References 35 publications

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

A Two-Coordinate Manganese(0) Complex with an Unsupported Mn–Mg Bond: Allowing Access to Low Coordinate Homo- and Heterobimetallic Compounds

The Reductive Activation of CO2Across a Ti═Ti Double Bond: Synthetic, Structural, and Mechanistic Studies

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The Reductive Activation of CO₂Across a Ti═Ti Double Bond: Synthetic, Structural, and Mechanistic Studies