Selective Preparation of Diamondoid Phosphonates

Fokin, Andrey A.; Yurchenko, R. I.; Tkachenko, Boryslav A.; Fokina, Natalie A.; Gunawan, Maria A.; Poinsot, Didier; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Serafin, Michael; Cattey, Hélène; Hierso, Jean‐Cyrille; Schreiner, Peter R.

doi:10.1021/jo500793m

Cited by 12 publications

(14 citation statements)

References 34 publications

(76 reference statements)

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“…Nucleation Densities from Diamondoid Monolayers. To test this concept for diamond, a silicon substrate was functionalized with a monolayer of phosphonyl dichloride (POCl 2 )-modified diamondoid protonuclei, which were covalently attached to the surface via P-O-Si bonds (29). PECVD diamond growth was then performed using standard conditions, resulting in different densities of large diamond particles depending on the size of the diamondoid seed (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The diamondoid order, N, is shown above each chemical name. Diamondoids were functionalized with POCl 2 self-assembly groups (29) for covalent attachment to PECVD substrates.…”

Section: Resultsmentioning

confidence: 99%

“…Mass spectrometry, gas chromatography, and NMR spectroscopy were used to ensure diamondoid purity. Diamondoid molecules were then selectively functionalized via multistep synthesis (29) to enable covalent attachment of diamondoid self-assembled monolayers on oxidized silicon surfaces. Adamantane was also functionalized with a 2(trichlorosilyl)ethyl group (SiCl 3 ) at the 1-position to assess the impact of attachment chemistry under the milder remote plasma CVD growth conditions.…”

Section: Methodsmentioning

confidence: 99%

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Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

Gebbie

Ishiwata

McQuade

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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Nucleation is a core scientific concept that describes the formation of new phases and materials. While classical nucleation theory is applied across wide-ranging fields, nucleation energy landscapes have never been directly measured at the atomic level, and experiments suggest that nucleation rates often greatly exceed the predictions of classical nucleation theory. Multistep nucleation via metastable states could explain unexpectedly rapid nucleation in many contexts, yet experimental energy landscapes supporting such mechanisms are scarce, particularly at nanoscale dimensions. In this work, we measured the nucleation energy landscape of diamond during chemical vapor deposition, using a series of diamondoid molecules as atomically defined protonuclei. We find that 26-carbon atom clusters, which do not contain a single bulk atom, are postcritical nuclei and measure the nucleation barrier to be more than four orders of magnitude smaller than prior bulk estimations. These data support both classical and nonclassical concepts for multistep nucleation and growth during the gas-phase synthesis of diamond and other semiconductors. More broadly, these measurements provide experimental evidence that agrees with recent conceptual proposals of multistep nucleation pathways with metastable molecular precursors in diverse processes, ranging from cloud formation to protein crystallization, and nanoparticle synthesis.

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Section: Resultsmentioning

confidence: 99%

“…The diamondoid order, N, is shown above each chemical name. Diamondoids were functionalized with POCl 2 self-assembly groups (29) for covalent attachment to PECVD substrates.…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

Gebbie

Ishiwata

McQuade

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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“…Hydroxydiamantanes 2a,b were converted to the corresponding chlorophosphonates 3ad, 3bd, 3ac, and 3bc through the phosphorylation reaction in trifluoroacetic acid [17,18] utilizing PhPCl 2 and AdPCl 2 as phosphorylating agents (Scheme 2). Chlorophosphonates 3ad, 3bd, 3ac, and 3bc were further reduced with LiAlH 4 in tetrahydrofuran to give phosphines 4ad, 4bd, 4ac, and 4bc.…”

Section: Resultsmentioning

confidence: 99%

“…Purify the crude product by column chromatography on silica (hexane − diethyl ether (2:1)) to give the corresponding diamantyl-1-adamantyl chlorophosphonate as colorless crystals. The NMR spectra of chlorophosphonates 3ac and 3bc were identical as previously described [18].…”

Section: Experimental Partmentioning

confidence: 99%

P-Stereogenic diamondoid phosphines

Butova¹,

Bahonsky²,

Yurchenko³

et al. 2020

J. org. pharm. chem.

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P-Stereogenic diamondoid phosphines Despite diamondoid phosphines have found many synthetic applications and are even available commercially the chemistry of chiral diamondoid phosphines remains largely unexplored. Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis. Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the reduction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enantiomers. Experimental part. The experimental procedures for the preparation of 1-and 4-diamantyl-1-adamantyland phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS spectral data. Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phosphines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is determined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis.

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Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

George

Dopfer

2022

Chemistry A European J

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Radical cations of diamondoids, a fundamental class of very stable cyclic hydrocarbon molecules, play an important role in their functionalization reactions and the chemistry of the interstellar medium. Herein, we characterize the structure, energy, and intermolecular interaction of clusters of the amantadine radical cation (Ama + , 1-aminoadamantane) with solvent molecules of different interaction strength by infrared photodissociation (IRPD) spectroscopy of massselected Ama + L n clusters, with L=Ar (n � 3) and L=N 2 and H 2 O (n = 1), and dispersion-corrected density functional theory calculations (B3LYPÀ D3/cc-pVTZ). Three isomers of Ama + generated by electron ionization are identified by the vibrational properties of their rather different NH 2 groups. The ligands bind preferentially to the acidic NH 2 protons, and the strength of the NH…L ionic H-bonds are probed by the solvation-induced red-shifts in the NH stretch modes. The three Ama + isomers include the most abundant canonical cage isomer (I) produced by vertical ionization, which is separated by appreciable barriers from two bicyclic distonic iminium ions obtained from cage-opening (primary radical II) and subsequent 1,2 H-shift (tertiary radical III), the latter of which is the global minimum on the Ama + potential energy surface. The effect of solvation on the energetics of the potential energy profile revealed by the calculations is consistent with the observed relative abundance of the three isomers. Comparison to the adamantane cation indicates that substitution of H by the electron-donating NH 2 group substantially lowers the barriers for the isomerization reaction.[a] M.

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Selective Preparation of Diamondoid Phosphonates

Cited by 12 publications

References 34 publications

Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

P-Stereogenic diamondoid phosphines

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

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Selective Preparation of Diamondoid Phosphonates

Cited by 12 publications

References 34 publications

Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

Experimental measurement of the diamond nucleation landscape reveals classical and nonclassical features

P-Stereogenic diamondoid phosphines

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N2, and H2O

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Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O