Naslov
Defying stereotypes with nanodiamonds: stable primary diamondoid phosphines

Autori
Moncea, Oana ; Šekutor, Marina ; Hausmann, Heike ; Gunawan, Maria ; Poinsot, Didier ; Fokin, Anrey A. ; Hierso, Jean-Cyrille ; Schreiner, Peter R.

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, ostalo

Izvornik
6th EuCheMS Chemistry Congress / - Sevilla, 2016, 1459-1459

Skup
6th EuCheMS Chemistry Congress

Mjesto i datum
Sevilla, Španjolska, 11.09.2016. - 15.09.2016

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
diamondoids ; stable phosphines ; bulky hydrocarbons

Sažetak
The widespread application of primary phosphines is still limited due to their high sensitivity towards oxidation, often resulting in pyrophoricity. Introduction of bulky substituents that can kinetically stabilize primary phosphines is one method for decreasing their oxygen sensitivity. Assessing the air sensitivity of such compounds is achieved by determination of their radical cation SOMO energies obtained by DFT computations. Diamondoids are bulky cage hydrocarbons that resemble the diamond crystal lattice. Functionalized diamondoids have found diverse applications ranging from medicinal chemistry to the material sciences. Their bulkiness also makes them ideal substituents for stabilizing primary phosphines since they can serve as excellent electron donors. We present here the synthesis of novel, air stable primary (and secondary) diamondoid phosphines prepared from diamondoid phosphonates. Their observed air stability was also confirmed by comparison of the computed radical cation SOMO energies. We found that more stable phosphines have SOMO energies higher than the proposed threshold of ‒10 eV, which is in agreement with the claim that primary phosphines with lower SOMO energies react with dioxygen readily. For example, primary diamantyl diphosphine is more stable than primary diamantyl monophosphine (–9.9 and –11.0 eV, respectively), as also observed experimentally. In addition, VT-NMR studies of selected diamondoid phosphines were also conducted to clarify the unusual signal behavior noticed in the 31P and 1H NMR spectra at room temperature.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

Napomena
Humboldt Research Fellowship for Postdoctoral Researchers

POVEZANOST RADA