A Persistent Dipotassium 1,2,4‐Diazaphospholide Radical Complex: Synthesis, X‐Ray Structure, and Bonding

Pi, Chengfu; Wang, Yan; Zheng, Wenjun; Wan, Li; Wu, Hongyu; Weng, Linhong; Wu, Limin; Li, Qianshu; Schleyer, Paul von Ragué

doi:10.1002/anie.200906303

Cited by 44 publications

(13 citation statements)

References 48 publications

(45 reference statements)

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“…To better understand the similarity/difference between the DBAP and the phenalenyl cation, chemical reduction of DBAP to its radical anion and dianion will be also conducted. Although a few π-conjugated polycyclic aromatics containing a four-π-electron heteronuclear (NBN/OBO/SBS) unit or simple monoheterocycles containing three heteroatoms (e.g., 1,2,4-diazaphosphole) have been reported (Figure a), much fewer studies have been performed on their open-shell radical ions , and doubly charged ions. Therefore, in this work, we will report the synthesis and physical characterizations of several DBAP derivatives and the corresponding anions.…”

Section: Introductionmentioning

confidence: 99%

B–N–B Bond Embedded Phenalenyl and Its Anions

et al. 2017

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Despite the great potential of heteroatom-containing polycyclic aromatic hydrocarbons in organic optoelectronics, there are very limited reports on heteroaromatics containing a B-N-B bond in the π-scaffold. Herein, stable 1,9-dibora-9a-azaphenalenyl (DBAP) derivatives, named BNB-embedded phenalenyls, are presented. The DBAP skeleton contains a three-center two-π-electron B-N-B moiety with 12 π-electrons and can be regarded as the isoelectronic structure of the phenalenyl cation. Chemical reduction of the phenyl derivative of DBAP by potassium generated the dianion containing 14 delocalized π-electrons, which can be regarded as the isoelectronic structure of the phenalenyl anion. The dianion is sandwiched and stabilized by two bulky [K([18]crown-6)] counterions according to its X-ray structure. However, its monoanion (an isoelectronic structure of the henalenyl radical) generated by mixing equal moles of neutral compound and dianion gave an unusual B-N-B-embedded benzo[cd]fluoranthene dianion, which again was confirmed by X-ray crystallographic analysis. The new dianion containing 20 π-electrons is highly aromatic and is further stabilized by [K([18]crown-6)] counterions. An aromaticity driven rearrangement mechanism was proposed for this unusual transformation. Based on X-ray structures and theoretical calculations, the B-N-B moiety in the neutral and anionic DBAP participates in the π-electron delocalization along the whole DBAP skeleton like their phenalenyl cation/radical/anion counterparts, but with more localized character. Therefore, our studies report the first synthesis and characterization of a B-N-B-embedded phenalenyl and its anionic species, which show unique electronic structure and unusual reactivity different from that of their all-carbon phenalenyl analogues.

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Section: Introductionmentioning

confidence: 99%

B–N–B Bond Embedded Phenalenyl and Its Anions

et al. 2017

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“…68 A persistent 1,2,4diazaphospholide dianion radical complex with a triple-decker conformation has been prepared by reduction of 1,2,4-diazaphospholide anion with potassium. 69 Four novel heterobimetallic sodium zincate complexes containing cis-2,6-dimethylpiperidide (cis-DMP) have been prepared and characterised. 37 Sodiummediated magnesiation has been employed to regioselectively metallate thiophene and tetrahydrothiophene at ambient temperature.…”

Section: Sodium Potassium Rubidium and Caesiummentioning

confidence: 99%

Alkaline and alkaline earth metals

Hill

2011

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Advances in the coordination and inorganic chemistry of the elements of Groups 1 and 2 of the periodic table from the calendar year 2010 are summarised in this non-critical review. As was the case in previous years, coverage concentrates on topics centred around the synthesis, structures and applications of coordination compounds and the organometallic chemistry of these elements. HighlightsThe isolation and reaction chemistry of kinetically-stabilised Group 2 species in which the alkaline earth centre exists in a formal +1 oxidation state has received intense international attention while interest in the potential of alkaline earth complexes as benign and inexpensive reagents for catalysis has continued to develop.

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“…[1] Despite the challenges to access stable or persistent radicals owing to the limited number of energetically accessible valence orbitals in main-group elements, a number of stable radicals based on main-group elements have been isolated. [1] Continuous efforts have led to the emergence of a variety of phosphoruscentered radicals, including neutral, [2] anionic, [3] and cationic species. [1] Continuous efforts have led to the emergence of a variety of phosphoruscentered radicals, including neutral, [2] anionic, [3] and cationic species.…”

mentioning

confidence: 99%

“…[1] Among them, Group 15 element-based radicals are attracting attention in current chemical research. [1] Continuous efforts have led to the emergence of a variety of phosphoruscentered radicals, including neutral, [2] anionic, [3] and cationic species. [4] Regarding radical cations, Bertrand and co-workers isolated a stable phosphaalkene radical cation, [4b] P 2 C + , [4c] and PNC +[4d] radical cations stabilized by N-heterocyclic carbenes (NHCs).…”

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confidence: 99%

Elusive Antimony‐Centered Radical Cations: Isolation, Characterization, Crystal Structures, and Reactivity Studies

Wei

Fang

et al. 2016

Angewandte Chemie

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One-electron oxidation of the stibines Aryl 3 Sb (1, Aryl = 2,6-i Pr 2 -4-OMe-C 6 H 2 ; 2, Aryl = 2,4,6-i Pr 3 -C 6 H 2 ) with AgSbF 6 and NaBAryl F 4 (Aryl F = 3,5-(CF 3 ) 2 C 6 H 3 ) afforded the first structurally characterized examples of antimony-centered radical cations 1C + [BAryl F 4 ] À and 2C + [BAryl F 4 ] À . Their molecular and electronic structures were investigated by singlecrystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/Vis absorption spectroscopy, in conjunction with theoretical calculations. Moreover, their reactivity was investigated. The reaction of 2C + [BAryl F 4 ] À and p-benzoquinone afforded a dinuclear antimony dication salt 3 2+ [BAryl F 4 ] 2 À , which was characterized by NMR spectroscopy and X-ray diffraction analysis. The formation of the dication 3 2+ further confirms that the isolated stibine radical cations are antimony-centered.

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A Persistent Dipotassium 1,2,4‐Diazaphospholide Radical Complex: Synthesis, X‐Ray Structure, and Bonding

Cited by 44 publications

References 48 publications

B–N–B Bond Embedded Phenalenyl and Its Anions

B–N–B Bond Embedded Phenalenyl and Its Anions

Alkaline and alkaline earth metals

Elusive Antimony‐Centered Radical Cations: Isolation, Characterization, Crystal Structures, and Reactivity Studies

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