Rhodium-katalysierte Bildung von Phosphor-Bor-Bindungen: Synthese des ersten Poly(phosphanylborans) mit hoher Molekülmasse

Dorn, Hendrik; Singh, Ryan A.; Massey, Jason A.; Lough, Alan J.; Manners, Ian

doi:10.1002/(sici)1521-3757(19991115)111:22<3540::aid-ange3540>3.0.co;2-j

Cited by 61 publications

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References 24 publications

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“…[15] All of the examples reveal the requirement of organic substituents for catenation. [17,18] Among the different structural motifs of oligophosphinoboranes only the ring systems (F, [19] G, [19c] and H [20] ) and the short four-membered chain I [21] have been characterized by Xray structural analysis for which the presence of organic substituents is very helpful. [16] Lewis acid-base adduct compounds for Group 13/15 elements of the type R 3 E·E'R 3 (E = Group 15 element, E' = Group 13 element) are electronically and structurally related to hydrocarbons.…”

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Cationic Chains of Phosphanyl‐ and Arsanylboranes

et al. 2014

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Whilst catena-phosphorus cations have been intensively studied in the last years, mixed Group 13/15 element cationic chains have not yet been reported. Reaction of the pnictogenboranes H2EBH2⋅NMe3 (E=P, As) with monohalideboranes lead to the cationic chain compounds [Me3N⋅BH2EH2BH2⋅NMe3][X] (E=P, As; X=AlCl4 , I) and [Me3N⋅BH2PH2BH2PH2BH2⋅NMe3][X] (X=I, VCl4(thf)2), respectively. All of the compounds have been characterized by X-ray structure analysis, NMR spectroscopy, IR spectroscopy, and mass spectrometry. DFT calculations elucidate the reaction pathway, the high thermodynamic stability, the charge distribution within the chain and confirm the observed solid-state structures.

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Cationic Chains of Phosphanyl‐ and Arsanylboranes

et al. 2014

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“…20−22 In the late 1990s, Manners et al reported the transition-metal-catalyzed dehydrocoupling of primary phosphine−borane adducts, which resulted in wellcharacterized, predominantly linear poly(phosphinoboranes), while secondary phosphine−borane adducts 23 gave dimers and six-or eight-membered rings (Scheme 1). 24,25 It was claimed earlier that the presence of amines promotes the formation of linear rather than cyclic products by coordination to the terminal BH 2 group. 26 For example, thermolysis of Me 2 P−PMe 2 −BH 3 or RMePH−BH 3 (R = Me or Et) at 175−200 °C in the presence of catalytic amounts of triethylamine gave polymers [RMeP−BH 2 ] n with molecular weights of 1800−6000 Da.…”

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Cross-dehydrocoupling: A Novel Synthetic Route to P–B–P–B Chains

2014

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Transition-metal-catalyzed dehydrocoupling of tert-butylferrocenylphosphine-borane (2) with [{Rh(μ-Cl)(1,5-cod)}2] (cod = cyclooctadiene) as the catalyst gave the homocoupled product [Fc(tBu)(H)P(BH2)P(Fc)(tBu)(BH2X)] [3; Fc = Fe(C5H5)(C5H4), X = H/Cl], while cross-dehydrocoupling with the tertiary phosphine-boranes P(tBu)(nBu)2(BH3) (2a) and PPh(nBu)2(BH3) (2b) using [Rh(1,5-cod)2]OTf (OTf = trifluoromethanesulfonate) gave the first cross-dehydrocoupled products reported to date, [Fc(tBu)(BH3)P(BH2)P(tBu)(nBu)2] (4) and [Fc(tBu)(BH3)P(BH2)PPh(nBu)2] (5), in moderate yields. Compounds 2-5 were characterized by NMR spectroscopy ((1)H, (13)C, (31)P, and (11)B), IR spectroscopy, mass spectrometry, and single-crystal X-ray structure determination.

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