Crystalline Boragermenes

Rao, Bin; Kinjo, Rei

doi:10.1002/anie.201914644

Cited by 27 publications

(24 citation statements)

References 65 publications

(12 reference statements)

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“… [10e] Kinjo has also recently shown that H 2 addition across a Ge=B double bond is possible. [21] It is worth noting that these examples all contain heteroatomic multiple bonds in which one of the elements has an n =2. We sought to map the reactivity of highly polarized heavier element multiple bonds by exploring the reactivity of compound A towards a range of compounds possessing E−H bonds (E=N, O, C, P, Si) of different polarity.…”

Section: Introductionmentioning

confidence: 99%

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Contrasting E−H Bond Activation Pathways of a Phosphanyl‐Phosphagallene

2021

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The reactivity of the phosphanyl‐phosphagallene, [H2C{N(Dipp)}]2PP=Ga(Nacnac) (Nacnac=HC[C(Me)N(Dipp)]2; Dipp=2,6‐iPr2C6H3) towards a series of reagents possessing E−H bonds (primary amines, ammonia, water, phenylacetylene, phenylphosphine, and phenylsilane) is reported. Two contrasting reaction pathways are observed, determined by the polarity of the E−H bonds of the substrates. In the case of protic reagents (δ−E−Hδ+), a frustrated Lewis pair type of mechanism is operational at room temperature, in which the gallium metal centre acts as a Lewis acid and the pendant phosphanyl moiety deprotonates the substrates. Interestingly, at elevated temperatures both NH2iPr and ammonia can react via a second, higher energy, pathway resulting in the hydroamination of the Ga=P bond. By contrast, with hydridic reagents (δ+E−Hδ−), such as phenylsilane, hydroelementation of the Ga=P bond is exclusively observed, in line with the polarisation of the Si−H and Ga=P bonds.

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Section: Introductionmentioning

confidence: 99%

“…Anionic aluminium‐imides have been shown to add H 2 across the Al=N bond [10e] . Kinjo has also recently shown that H 2 addition across a Ge=B double bond is possible [21] . It is worth noting that these examples all contain heteroatomic multiple bonds in which one of the elements has an n =2.…”

Section: Introductionmentioning

confidence: 99%

Contrasting E−H Bond Activation Pathways of a Phosphanyl‐Phosphagallene

2021

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“…Borylenes, the boron analogs of carbenes, feature two empty orbitals and one lone pair of electrons on their boron centers (Chart ) and are highly reactive species . In addition to a plethora of examples of borylenes stabilized by coordination to transition metals, borylenes can also be stabilized by Lewis bases. , Lewis base-stabilized borylenes, both mono(Lewis base)- and bis(Lewis base)-stabilized examples, have been reported to be capable of fixing or functionalizing small molecules, such as H 2 , CO, , or even N 2 , as well as cleaving C–H, , C–C, ,, and B–H bonds. A number of bis(Lewis base)-stabilized borylenes have been synthesized and isolated since the first report of such a species by Bertrand and co-workers in 2011 .…”

Section: Introductionmentioning

confidence: 99%

C–C versus C–H Activation: Understanding How the Carbene π-Accepting Ability Controls the Intramolecular Reactivities of Mono(carbene)-Stabilized Borylenes

Dewhurst

Braunschweig

et al. 2021

Organometallics

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Highly reactive dicoordinate (i.e., mono-base-stabilized) borylenes of the form [LBR] (L = Lewis base) have recently shown intriguing reactivity with inert small molecules, including N2. However, this reactivity is complicated by competing intramolecular C–H and C–C bond activation reactions. In this work, density functional theory (DFT) calculations are performed to study the mechanisms of the selective intramolecular activation of ortho C(sp2)–C(sp3) and benzylic C(sp3)–H bonds of the N-bound aryl group of N-heterocyclic carbene (NHC) and cyclic (alkyl)(amino)carbene (CAAC) ligands observed experimentally in mono(carbene)-stabilized aminoborylenes. We focus our efforts on how different cyclic carbene ligands steer the selectivity of the reaction pathways, as well as the reaction products. The electronic structure analyses reveal that the “empty” p orbital and the “lone pair” of electrons located on the mono(carbene)-stabilized borylene boron center play important roles in determining the selectivity. The computational results indicate that the electron-pair acceptor capability of the former and the electron-pair donor capability of the latter are significantly affected by the attachment of different NHC ligands. The detailed mechanisms obtained lead to an in-depth understanding of the nature of the cleavage of ortho C(sp2)–C(sp3), C(sp2)–H, and benzylic C(sp3)–H bonds and the reactivity of different mono(carbene)-stabilized borylene compounds. The results have direct relevance to the exciting recent discoveries in the field of single-site main-group ambiphiles and their potential for small-molecule activation and catalysis.

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“…Previous examples of homoatomic heavy element multiple bonds have shown that homolytic cleavage is possible, however to our knowledge there have been no examples of a heavy heteroatomic multiple bond capable of heterolytic hydrogen activation. [20,21] Exposure of a solution containing 1 b to 2 bar of H 2 resulted in an immediate formation of 3 (Scheme 2). The 31 P NMR spectrum indicated quantitative formation of a new product with a doublet of doublets resonance at 67.0 ppm ( 1 J P-P = 578 Hz, 1 J P-H = 457 Hz), corresponding to the phosphanyl phosphorus atom, and a broad doublet resonance at À248.7 ppm ( 1 J P-P = 578 Hz), corresponding to the phosphinidene phosphorus atom.…”

Section: Angewandte Chemiementioning

confidence: 99%

A Phosphanyl‐Phosphagallene that Functions as a Frustrated Lewis Pair

2020

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Phosphagallenes (1 a/1 b) featuring double bonds between phosphorus and gallium were synthesized by reaction of (phosphanyl)phosphaketenes with the gallium carbenoid Ga(Nacnac) (Nacnac=HC[C(Me)N(2,6‐i‐Pr2C6H3)]2). The stability of these species is dependent on the saturation of the phosphanyl moiety. 1 a, which bears an unsaturated phosphanyl ring, rearranges in solution to yield a spirocyclic compound (2) which contains a P=P bond. The saturated variant 1 b is stable even at elevated temperatures. 1 b behaves as a frustrated Lewis pair capable of activation of H2 and forms a 1:1 adduct with CO2.

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Crystalline Boragermenes

Cited by 27 publications

References 65 publications

Contrasting E−H Bond Activation Pathways of a Phosphanyl‐Phosphagallene

Contrasting E−H Bond Activation Pathways of a Phosphanyl‐Phosphagallene

C–C versus C–H Activation: Understanding How the Carbene π-Accepting Ability Controls the Intramolecular Reactivities of Mono(carbene)-Stabilized Borylenes

A Phosphanyl‐Phosphagallene that Functions as a Frustrated Lewis Pair

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