Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes

Hadlington, Terrance J.; Szilvási, Tibor

doi:10.1038/s41467-022-28095-0

Cited by 17 publications

(23 citation statements)

References 52 publications

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“…This value is extremely close to that predicted by previous computational investigations of this compound (2.041 to 2.077 Å) ( 7 – 9 ). Examples of hydride-bridged beryllium compounds of the form XBe(μ-H) 2 BeX all feature wider Be – Be separations [range, 2.098(3) to 2.212(8) Å; mean, 2.136 Å] ( 26 , 30 – 32 ). The Be–C distances within 2 range from 1.923(2) to 1.938(2) Å (mean, 1.930 Å) and are considerably longer than that of BeCp 2 [range, 1.862(9) to 1.936(8) Å; mean, 1.904 Å] ( 28 ).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…The 1 H NMR spectrum of 2 consists of a single resonance at 5.73 parts per million (ppm), which corresponds to the five equivalent cyclopentadienyl ligand protons. The 1 H NMR resonances of terminal beryllium-bound hydride ligands are generally found between 4 and 5 ppm ( 32 , 33 ). Thus, 2 shows no signals attributable to Be–H hydrides in its 1 H NMR spectrum, only the resonance that corresponds to the cyclopentadienyl ligand.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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Diberyllocene, a stable compound of Be(I) with a Be–Be bond

Boronski¹,

Crumpton²,

Wales³

et al. 2023

Science

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The complex diberyllocene, CpBeBeCp (Cp, cyclopentadienyl anion), has been the subject of numerous chemical investigations over the past five decades yet has eluded experimental characterization. We report the preparation and isolation of the compound by the reduction of beryllocene (BeCp 2 ) with a dimeric magnesium(I) complex and determination of its structure in the solid state by means of x-ray crystallography. Diberyllocene acts as a reductant in reactions that form beryllium-aluminum and beryllium-zinc bonds. Quantum chemical calculations indicate parallels between the electronic structure of diberyllocene and the simple homodiatomic species diberyllium (Be 2 ).

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Section: Synthesis and Characterizationmentioning

confidence: 99%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Diberyllocene, a stable compound of Be(I) with a Be–Be bond

Boronski¹,

Crumpton²,

Wales³

et al. 2023

Science

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“… For example, compounds with covalent bonds between beryllium and electropositive elements, such as aluminium and boron, have been reported, as have compounds that feature BeC and BeN double bonds (Figure A–C). − Complexes that can even be considered to contain the metal in the 0 or +1 oxidation state have been reported (Figure D,E), although alternative descriptions of these systems have also been proposed . Indeed, conclusive evidence of these compounds reacting as sources of low-valent beryllium has yet to be reported. , …”

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confidence: 99%

Inducing Nucleophilic Reactivity at Beryllium with an Aluminyl Ligand

et al. 2023

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The reactions of anionic aluminium or gallium nucleophiles {K[E(NON)]}2 (E = Al, 1; Ga, 2; NON = 4,5-bis(2,6-diisopropylanilido)-2,7-ditert-butyl-9,9-dimethylxanthene) with beryllocene (BeCp2) led to the displacement of one cyclopentadienyl ligand at beryllium and the formation of compounds containing Be–Al or Be–Ga bonds (NON)EBeCp (E = Al, 3; Ga, 4). The Be–Al bond in the beryllium–aluminyl complex [2.310(4) Å] is much shorter than that found in the small number of previous examples [2.368(2) to 2.432(6) Å], and quantum chemical calculations suggest the existence of a non-nuclear attractor (NNA) for the Be–Al interaction. This represents the first example of a NNA for a heteroatomic interaction in an isolated molecular complex. As a result of this unusual electronic structure and the similarity in the Pauling electronegativities of beryllium and aluminium, the charge at the beryllium center (+1.39) in 3 is calculated to be less positive than that of the aluminium center (+1.88). This calculated charge distribution suggests the possibility for nucleophilic behavior at beryllium and correlates with the observed reactivity of the beryllium–aluminyl complex with N,N′-diisopropylcarbodiimidethe electrophilic carbon center of the carbodiimide undergoes nucleophilic attack by beryllium, thereby yielding a beryllium–diaminocarbene complex.

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“…[26] We [21] and others [27] have shown that the formyl ligand can be stabilised through resonance with the corresponding oxycarbene structure (Figure 1). [28] Figure 1. Canonical forms of a metal-formyl complex and reported structural motifs formed via metal-formyl intermediates.…”

Section: Structural Motifs From Co and H -mentioning

confidence: 99%

Carbon–Carbon Bond Formation from CO and H– The Role of Metal Formyl Intermediates

Parr

Crimmin

2022

Preprint

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In this mini-review, we summarise the current examples of carbon chain production from metal formyl intermediates with homogeneous metal complexes. To date, the formation of both unsaturated and saturated C2 motifs along with cyclic C3 products has been reported. We discuss the mechanistic aspects of these reactions and the challenges and opportunities in using this understanding to underpin future FT chemistry.

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Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes

Cited by 17 publications

References 52 publications

Diberyllocene, a stable compound of Be(I) with a Be–Be bond

Diberyllocene, a stable compound of Be(I) with a Be–Be bond

Inducing Nucleophilic Reactivity at Beryllium with an Aluminyl Ligand

Carbon–Carbon Bond Formation from CO and H– The Role of Metal Formyl Intermediates

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