Syntheses of a stable tristibine and of related antimony compounds with the 2,6-dimesitylphenyl (Dmp) substituent

Breunig, H. J.; Lork, Enno; Moldovan, Ovidiu; Raţ, Ciprian I.

doi:10.1016/j.jorganchem.2008.04.038

Cited by 28 publications

(18 citation statements)

References 23 publications

(39 reference statements)

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“…The SbPh 2 OH and Cl ligands occupy equatorial positions. The presence of an SbeOH moiety supports our belief that 5 contains an SbeCl group which probably underwent hydrolysis during TLC separation on silica; a similar hydrolysis of an SbeBr bond during TLC separation has been observed previously [8]. This hydrolysis reaction may also account for the small amount of 6a which cocrystallised out; excess/residual PhICl 2 , or HCl resulting from the hydrolysis of 5b, would have converted the terminal hydride to a chloro ligand [9].…”

Section: Resultssupporting

confidence: 80%

Oxidative addition of halogen across an Os-Os or Os-Sb bond: Formation of five-membered osmium-antimony carbonyl rings

Ganguly

Leong

2016

Journal of Organometallic Chemistry

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Section: Resultssupporting

confidence: 80%

Oxidative addition of halogen across an Os-Os or Os-Sb bond: Formation of five-membered osmium-antimony carbonyl rings

Ganguly

Leong

2016

Journal of Organometallic Chemistry

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“…These reactions proceeded in reasonable isolated yield for 3 b (77 %) and 3 c (58 %) but 3 a proved to be a thermally unstable oil, which could only be spectroscopically characterized in freshly made solutions before extensive decomposition occurred denoted by loss of metallic Sb. Two attempts were made to obtain single crystals of 3 a by rigorous cryogenic handling (−25 °C throughout) but in both cases, only a few crystals of the distibine 4 were isolated (Figure S3), suggesting that dehydrogenative coupling is at least partly responsible for the observed thermal instability of this compound (Scheme b). In contrast, hydrides 3 b and 3 c are air‐sensitive but indefinitely stable under an inert atmosphere of dry and deoxygenated nitrogen in the solid phase and in non‐halogenated solvents.…”

Section: Resultsmentioning

confidence: 99%

Hydrostibination

et al. 2019

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A rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p‐block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.

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“…Breunig, Tokitoh, Scheer, Power, and we have shown that primary and secondary stibines can be deprotonated in the presence of alkyllithium bases, amino bases, and alkali metals. 26,[33][34][35][36][37][38][39] In contrast, Huang has implied hydride-like reactivity for Ph2SbH in AlCl3-catalyzed hydrostibination of C=O bonds. 22 We and others have previously shown that stibines react with the trityl cation Ph3C + to yield Ph3C-H and stibenium ions, further evidencing hydridic reactivity for the Sb-H bond.…”

Section: Considered Mechanismsmentioning

confidence: 99%

Hydrostibination of Alkynes: A Radical Mechanism

MacMillan¹,

Marczenko²,

Johnson³

et al. 2020

Preprint

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The addition of Sb-H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov Z-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring neutral radical SbII and SbIII intermediates. Density Functional Theory (DFT) calculations are consistent this model, predicting an activation barrier that is within 1 kcal mol-1 of the experimental value (Eyring analysis) and a rate limiting step that is congruent with experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring SbII and SbIII intermediates to yield the observed Z-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a methodology for accessing challenging products such as E-olefins.

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Syntheses of a stable tristibine and of related antimony compounds with the 2,6-dimesitylphenyl (Dmp) substituent

Cited by 28 publications

References 23 publications

Oxidative addition of halogen across an Os-Os or Os-Sb bond: Formation of five-membered osmium-antimony carbonyl rings

Oxidative addition of halogen across an Os-Os or Os-Sb bond: Formation of five-membered osmium-antimony carbonyl rings

Hydrostibination

Hydrostibination of Alkynes: A Radical Mechanism

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