Small molecule activation by well-defined compounds of heavy p-block elements

Oberdorf, Kai; Lichtenberg, Crispin

doi:10.1039/d3cc02190d

Cited by 25 publications

(11 citation statements)

References 152 publications

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“…[117] Besides elemental sulfur and phosphorus, a wide range of bismuth compounds have been reported to activate various small inorganic molecules, although in most cases the radical or polar nature of the involved process has not been studied in detail. [118] For example, Lichtenberg and coworkers reported the radical insertion of CO into a BiÀ N bond, [119] and several groups revealed the ability of different bismuth complexes to activate CO 2 . [120] Both the insertion [121] and extrusion [122] of SO 2 on BiÀ C bonds have been reported, and the insertion of CO 2 , COS and NO was also accomplished using highly polarized complex 51 (see Section 3.2, Scheme 12).…”

Section: Radical Bond Activation Mediated By Bismuthmentioning

confidence: 99%

Bismuth in Radical Chemistry and Catalysis

Mato,

Cornella

2023

Angew Chem Int Ed

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Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19th century, the preparation and characterization of both transient and persistent bismuth‐radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main‐group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth‐radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry. In this review, we delve into the milestones that eventually led to the present state‐of‐the‐art in the field of radical bismuth chemistry. Our focus aims at outlining the intrinsic discoveries in fundamental inorganic/organometallic chemistry and contextualizing their practical applications in organic synthesis and catalysis.

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Section: Radical Bond Activation Mediated By Bismuthmentioning

confidence: 99%

Bismuth in Radical Chemistry and Catalysis

Mato,

Cornella

2023

Angew Chem Int Ed

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“…18 h) at 80 °C to give a dark green solution. 1 H NMR spectrum showed full consumption of the starting material. The NMR tube was taken into a glovebox and the tap removed slowly to relieve pressure (from nitrogen evolution).…”

Section: Synthesis Of Al(non)(n = Flu)(dmap) (2•dmap)mentioning

confidence: 99%

“…Accurate elemental analysis data could not be obtained. 1 H NMR (500 MHz, C 6 D 6 ): δ 7.34 (dd, J = 6.8, 3.0, 2H, C 6 H 3 ), 7.30-7.24 (m, 4H, C 6 H 3 ), 7.18 (d, J = 7.8, 2H, C 13 H 8 ), 6.98 (t, J = 7.4, 2H, C 13 H 8 ), 6.92 (t, J = 7.4, 2H, C 13 H 8 ), 5.83 (d, J = 7.4, 2H, C 13 H 8 ), 5.07 (s, 1H, Flu-CH), 4.29 (sept, J = 6.8, 2H, CHMe 2 ), 4.11 (sept, J = 6.8, 2H, CHMe 2 ), 3.53 (s, 6H, THF), 3.37 (sept, J = 6.6, 1H, CHMe 2 ), 1.50 (d, J = 6.8, 6H, CHMe 2 ), 1.45 (d, J = 6.8, 6H, CHMe 2 ), 1.40 (s, 6H, THF), 1.29-1.23 (m, 18H, CHMe 2 ), 0.59 (s, 6H, NCMe 2 ), 0.54 (s, 6H, SiMe 2 ), 0.38 (s, 6H, SiMe 2 ). 13…”

Section: Synthesis Of Al(non){iprnc(n = Cme 2 )Nc(h)flu)} (4)mentioning

confidence: 99%

“…In recent years the application of low valent main group complexes for the activation of small molecules has emerged as a fundamental area of scientific research. [1] In many regards, the reactivity of these compounds may be considered as being equivalent to (or in some cases surpassing) that of the more traditionally studied transition metal complexes. [2] Aluminyl systems, comprised of a negatively charged Al(I) component charge balanced by a group 1 metal cation, are a family of highly reactive main-group compounds that have recently been established in this respect.…”

Section: Introductionmentioning

confidence: 99%

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Reductive Coupling of a Diazoalkane Derivative Promoted by a Potassium Aluminyl and Elimination of Dinitrogen to Generate a Reactive Aluminium Ketimide

Evans,

Anker,

McMullin

et al. 2023

Chemistry A European J

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The reaction of 9‐diazo‐9H‐fluorene (fluN2) with the potassium aluminyl K[Al(NON)] ([NON]2– = [O(SiMe2NDipp)2]2–, Dipp = 2,6‐iPr2C6H3) affords K[Al(NON)(κN1,N3‐{(fluN2)2})] (1). Structural analysis shows a near planar 1,4‐di(9H‐fluoren‐9ylidene)tetraazadiide ligand that chelates to the aluminium. The thermally induced elimination of dinitrogen from 1 affords the neutral aluminium ketimide complex, Al(NON)(N=flu)(THF) (2) and the 1,2di(9H‐fluoren‐9‐yl)diazene dianion as the potassium salt, [K2(THF)3][fluN=Nflu] (3). The reaction of 2 with N,N'diisopropylcarbodiimide (iPrN=C=NiPr) affords the aluminium guanidinate complex, Al(NON){N(iPr)C(N=CMe2)N(CHflu)} (4), showing a rare example of reactivity at a metal ketimide ligand. Density functional theory (DFT) calculations have been used to examine the bonding in the newly formed [(fluN2)2]2– ligand in 1 and the ketimide bonding in 2. The mechanism leading to the formation of 4 has also been studied using this technique.

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“…The recent interest in Main Group chemistry is driven by the search for unprecedented bonding and reactivity toward small molecules, 1,2 leading to cheaper and more sustainable alternatives to 2 nd and 3 rd row transition metal catalysts. 3 Transition-metal complexes dominate modern organic synthesis with their effectiveness in bond activation stemming from a small HOMO and LUMO gap and the ability to open up coordination sites, properties usually not associated with Main-Group compounds.…”

mentioning

confidence: 99%