1,4-Phenylen-bis-diphenylderivate der Elemente der 5. Hauptgruppe des Periodensystems

Zorn, H.; Schindlbauer, H.; Hammer, Dorothea

doi:10.1007/bf00901377

Cited by 16 publications

(6 citation statements)

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“…Thus, the synthesis of p -bis(diphenylbismuthino)benzene ( 2a ) was first investigated. In the previous synthesis of 2a , Zorn et al reacted Ph 2 BiCl with p -dilithiobenzene, in situ generated from p -dibromobenzene and n -BuLi in petroleum ether, and obtained the expected product in 14−20% yield . Other products were not given in their report.…”

Section: Resultsmentioning

confidence: 98%

“…To look into the basic optical property, UV−vis spectra of compounds 1 − 7 and Ph 3 BiCl 2 ( 8 ) were measured (Table ) . Zorn et al reported that the absorption maxima of 2a in EtOH was not so different from those of triphenylbismuthane 1 , although their extinction coefficients were considerably different . In accord with this, the increase in number of bismuth atoms from two to four did not change the absorption maxima so much for a series of para - and meta -phenylene-bridged bismuthanes 2 − 4 , indicating that the introduction of the phenylene bridges did not affect significantly the strength of the Bi−C bond nor the extent of delocalization of π electrons over the molecules.…”

Section: Resultsmentioning

confidence: 99%

“…Bi 2 -Bismuthane 2a: mp 158−160 °C (lit., 160−162 °C); 1 H NMR δ 7.34 (m, 12H), 7.73 (dd, 8H, J = 1.5, 7.6), 7.75 (s, 4H); δ C 127.7, 130.5, 137.6, 139.5, 154.5−155.5 (broad); FABMS m / z 803 ([M + H] + ), 725, 571, 495, 439, 307. Anal.…”

Section: Methodsmentioning

confidence: 99%

“…The extinction coefficients of two characteristic bands at λ max 248 and 280 nm for 1 (in EtOH) were ε = 1.29 × 10 4 and 0.42 × 10 4 ,23c while those at λ max 248 and 279 nm for 2a (in EtOH) were ε = 4.0 × 10 4 and 2.1 × 10 4 , respectively …”

Section: Referencesmentioning

confidence: 95%

“…However, little or no information is available at present for the bismuth counterparts due to the lack of convenient methodology for the synthesis of this class of compounds . Most known organopolybismuth compounds bear two bismuth atoms in a molecule, as shown by R 2 Bi−BiR 2 , ArBiBiAr, R 2 BiC⋮ CBiR 2 , p -Ph 2 BiC 6 H 4 BiPh 2 , Ph 2 BiS(CH 2 ) 5 SBiPh 2 , R 2 Bi(CH 2 ) n BiR 2 , 2d, R 2 BiEBiR 2 (E = O, S, Se, Te), 2h, p -Ph 2 BiOC 6 H 4 OBiPh 2 ,2d triptycene-like Bi 2 -bismuthanes, polysilylated Bi 2 -bismuthanes, a biphenylene-bridged Bi 2 -bismuthane, p -Ph 2 Bi(Br) 2 C 6 H 4 Bi(Br) 2 Ph 2 , and (Ph 3 BiX) 2 O 12 (hereafter n in Bi n denotes the number of bismuth atoms present in a molecule). From practical as well as theoretical points of view, syntheses of a series of thermally and kinetically stabilized oligomeric bismuth compounds bearing more than two bismuth atoms are of interest, since they would provide key information regarding the basic property of the bismuth-containing polymers .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes

Matano¹,

Kurata²,

Murafuji³

et al. 1998

Organometallics

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A series of meta- and para-phenylene-bridged Bi(III) n and Bi(V) n compounds (n ≥ 2) have been synthesized. Reaction of Ph2BiX (X = Cl, OSO2CF3) with p-Li2C6H4, p-(BrMg)2C6H4, or p- and m-(Me2S·Cu)2C6H4 generated in situ from dibromobenzenes gave the corresponding para- and meta-phenylene-bridged Bi n −bismuthanes, Ph2BiC6H4BiPh2 (2), Ph2BiC6H4Bi(Ph)C6H4BiPh2 (3), and Ph2BiC6H4Bi(Ph)C6H4Bi(Ph)C6H4BiPh2 (4), in 2−30% yields. Bi n -bismuthanes 2−4 were oxidatively chlorinated by SO2Cl2 to yield the Bi n -bismuth polychlorides 5−7, in which all pentavalent bismuth atoms bore three aryl groups and two chlorine atoms. Compounds 2−7 showed λmax at around 244−249 and 285−290 nm in the UV−vis spectra, suggesting that the phenylene bridges did not perturb significantly the σ- and π-transitions of the aromatic systems in these bismuth oligomers. Ortho-lithiation directed by the sulfonyl group was employed for the one-pot preparation of highly branched Bi n -bismuthanes; successive treatment of Ar3Bi 9a with 3 equiv of t-BuLi and Ar2BiI (10b) (Ar = 2-Et2NSO2C6H4) afforded m-phenylene-bridged Bi n -bismuthanes, Ar2Ar‘Bi (11a), ArAr‘2Bi (12a), and Ar‘3Bi (13a) in 2−49% yields (Ar‘ = 3-Ar2Bi-2-Et2NSO2C6H3). Treatment of ortho-lithiated (2-t-BuSO2C6H4)(p-Tol)2Bi (14) with p-Tol2BiCl gave sulfone-substituted Bi2-bismuthane 15, which was converted to the corresponding Bi2-chlorodiarylbismuthane (16) by the Bi−C cleavage reaction. An X-ray diffraction analysis of 16 showed that both bismuth centers have a distorted trigonal pyramidal geometry weakly coordinated by the neighboring sulfonyl-oxygen atoms. The symmetrically branched Bi4-bismuthane 13a was successfully converted to a dendritic Bi10-bismuthane 17 in 20% isolated yield by successive treatment with t-BuLi and 10b. The reaction between ortho-lithiated 9a and ArBiI2 (10c) followed by GPC separation afforded two fractions of oligomeric Bi n -bismuthanes, the vapor depression measurement of which revealed that the average numbers of the bismuth atoms present therein were 7 and 16, respectively. UV−vis spectra of 9a, 11a, 12a, 13a, and 17 exhibited no bathochromic shift; the inefficient π-electron delocalization would probably be due to the twisted geometry between aromatic rings, as inferred from the X-ray structure of the related Bi2-bismuthane 16. The extinction coefficients of these phenylene-bridged Bi n -bismuthanes were found to increase with increasing number of bismuth atoms.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Referencesmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes

Matano¹,

Kurata²,

Murafuji³

et al. 1998

Organometallics

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Nitrogen‐Containing Oligomers

Groenendaal¹,

Meijer²,

Vekemans³

1998

Electronic Materials: The Oligomer Approach

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Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen

Stoy,

Jürgensen,

Millidoni

et al. 2023

Angewandte Chemie

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Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate novel structural motifs in an operationally simple approach, which are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p‐block elements, albeit heavier p‐block elements show low bond dissociation energies and appear to be ideally suited for this approach. Here we show that a dinuclear organometallic bismuth compound, containing BiMe2 groups that are connected by a thioxanthene linker, readily undergoes selective and reversible cleavage of its Bi–C bonds upon exposure to external stimuli. The exploitation of DCvC in the field of organometallic heavy p‐block chemistry grants access to unprecedented macrocyclic and barrel‐type oligonuclear compounds.

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1,4-Phenylen-bis-diphenylderivate der Elemente der 5. Hauptgruppe des Periodensystems

Cited by 16 publications

References 0 publications

Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes

Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes

Nitrogen‐Containing Oligomers

Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen

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1,4-Phenylen-bis-diphenylderivate der Elemente der 5. Hauptgruppe des Periodensystems

Cited by 16 publications

References 0 publications

Synthesis and Properties of a Series of Phenylene-Bridged Bin-Bismuthanes

Synthesis and Properties of a Series of Phenylene-Bridged Bin-Bismuthanes

Nitrogen‐Containing Oligomers

Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen

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Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes

Synthesis and Properties of a Series of Phenylene-Bridged Bi_n-Bismuthanes