Probing Radical Addition to 1-Phosphabutadienes by Employing Muonium as a "Light Isotope" of Hydrogen.

Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (µSR) is a highly sensitive method that can detect radical species at 106 spins (cf. EPR: 1012 spins, NMR: 1018 spins). Herein, we employ µSR to detect the radical-addition products from three 1-phosphabutadiene monomers, P-analogues of isoprene. We show that muonium (Mu), a "light" H-atom surrogate, adds predominantly at the C4 position of the P1 =C2 -C3 =C4 moiety to give unprecedented 1-phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT-calculations. A minor radical product is also detected that is tentatively assigned to an PC3 -heterocyclic free radical. On the basis of DFT-predictions, we speculate that its formation may involve initial addition of Mu+ at the C3 position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1-phosphabutadienes, which have previously been polymerized using anionic initiation.

The Reaction of Muonium with Hydrogen Peroxide in Aqueous Solution.

Rate constants for the reactions of muonium (Mu) (the ultralight isotope of the hydrogen atom) with H2 O2 in H2 O and D2 O2 in D2 O have been determined at various temperatures and pH (pD) values. The data are consistent with the three reactions: Mu + H 2 O 2 → k 1 M products ${{\rm{Mu}} + {\rm{H}}_2 {\rm{O}}_2 \mathop \rightarrow \limits ^{{k_{1{\rm{M}}} }}_{} {\rm{products}}}$ , Mu + HO 2 - → k 2 M products ${{\rm{Mu}} + {\rm{HO}}_2^ - \mathop \rightarrow \limits ^{{k_{2{\rm{M}}} }}_{} {\rm{products}}}$ , Mu + O - → k 3 M products ${{\rm{Mu}} + {\rm{O}}^ - \mathop \rightarrow \limits ^{{k_{3{\rm{M}}} }}_{} {\rm{products}}}$ and the equivalent for the deuterated entities. A significant positive H/D isotope effect was found for the undissociated peroxide, while for the anions the effect was negligible or slightly in the opposite direction. In addition, for concentrated solutions of peroxide a study of the muon spin polarization as a function of applied transverse magnetic field yielded results consistent with the rate constants determined from the direct decay measurements, and indicated that the reaction products are diamagnetic, most likely MuH and MuOH, i. e., no muoniated radical products are formed. These results are potentially relevant for management of the radiolysis products in nuclear industry.

Free Radicals Formed by H Atom Addition to Allenes as Determined by Muon Spin Spectroscopy.

Allyl and vinyl radicals are important intermediates in diverse areas of chemistry, ranging from combustion to synthesis. However, questions remain about the competitive formation of these radicals from allenes. Here, we present a study of prototypical allyl and vinyl radicals formed by H atom addition to allenes. They were studied by forming the analogous muonium adducts because muonium (Mu) behaves as a light isotope of hydrogen, and muoniated species can be characterized by muon spin spectroscopy (µSR). Two techniques were employed: transverse-field muon spin rotation (TF-µSR) and muon level-crossing resonance (µLCR), which allow for the measurement of muon hyperfine constants (hfcs) and other nuclear hfcs, respectively, and thus aid identification of the formed radicals. TF-µSR has already been used to determine that two radicals are formed by Mu addition to 1,1-dimethylallene, but µLCR techniques were undeveloped at the time of that study, so assignments were based on electron spin resonance (ESR) data of similar allyl and vinyl radicals. We report here the µSR of multiple radicals detected from positive muon irradiation of 1,1-dimethylallene and 1-methoxyallene in solution. The radicals were identified by comparison of muon and proton hfcs with ESR data and the results of density functional theory calculations. The conclusion is that muonium (and by extension, the H atom) can add to all three carbons of the allene system, albeit with preference for the central carbon.

Free Radical Chemistry of Phosphasilenes.

Understanding the characteristics of radicals formed from silicon-containing heavy analogues of alkenes is of great importance for their application in radical polymerization. Steric and electronic substituent effects in compounds such as phosphasilenes not only stabilize the Si=P double bond, but also influence the structure and species of the formed radicals. Herein we report our first investigations of radicals derived from phosphasilenes with Mes, Tip, Dur, and NMe2 substituents on the P atom, using muon spin spectroscopy and DFT calculations. Adding muonium (a light isotope of hydrogen) to phosphasilenes reveals that: a) the electron-donor NMe2 and the bulkiest Tip-substituted phosphasilenes form several muoniated radicals with different rotamer conformations; b) bulky Dur-substituted phosphasilene forms two radicals (Si- and P-centred); and c) Mes-substituted phosphasilene mainly forms one species of radical, at the P centre. These significant differences result from intramolecular substituent effects.

Free Radical Reactivity of a Phosphaalkene Explored Through Studies of Radical Isotopologues.

Muonium (Mu), an H atom analogue, is employed to probe the addition of free radicals to the P=C bond of a phosphaalkene. Specifically, two unprecedented muoniated free radicals, MesP. -CMu(Me)2 (1 a, minor product) and MesPMu-C. Me2 (1 b, major product), were detected by muon spin spectroscopy (µSR) when a solution of MesP=CMe2 (1: Mes=2,4,6-trimethylphenyl) was exposed to a beam of positive muons (µ+ ). The µ+ serves as a source of Mu (that is, Mu=µ+ +e- ). To confirm the identity of the major product 1 b, its spectral features were compared to its isotopologue, MesPH-C. (Me)CH2 Mu (2 a). Conveniently, 2 a is the sole product of the reaction of MesPH(CMe=CH2 ) (2) with Mu. For all observed radicals, muon, proton, and phosphorus hyperfine coupling constants were determined by µSR and compared to DFT-calculated values.

Characterization of Free Radicals in Clathrate Hydrates of Furan, 2,3-Dihydrofuran, and 2,5-Dihydrofuran by Muon Spin Spectroscopy.

In addition to their importance as abundant hydrocarbon deposits in nature, clathrate hydrates are being studied as potential media for hydrogen and carbon dioxide storage and as "nano-reactors" for small molecules. However, little is known about the behavior of reactive species in such materials. We have employed muon spin spectroscopy to characterize various organic free radicals that reside as isolated guests in structure II clathrates. The radicals are formed by reaction of atomic muonium (Mu) with the guest molecules furan and two isomeric dihydrofurans. Muonium is essentially a light isotope of hydrogen and adds to unsaturated molecules in the same manner as H. We have determined muon and proton hyperfine coupling constants for the muoniated radicals formed in the clathrates and also in neat liquids at the same temperature. DFT calculations were used to guide the spectral assignments and distinguish between competing radical products for Mu addition to furan and 2,3-dihydrofuran. Relative signal amplitudes provide yields and thus the relative reactivities of the C4 and C5 addition sites in these molecules. Spectral features, hyperfine constants, and reactivities all indicate that the radicals do not tumble freely in the clathrate cages in the same way that they do in liquids.

Proton, muon and ¹³C hyperfine coupling constants of C60X and C70X (X = H, Mu).

The reaction of H atoms with fullerene C70 has been investigated by identifying the radical products formed by addition of the atom muonium (Mu) to the fullerene in solution. Four of the five possible radical isomers of C70Mu were detected by avoided level-crossing resonance (µLCR) spectroscopy, using a dilute solution of enriched (13)C70 in decalin. DFT calculations were used to predict muon and (13)C isotropic hyperfine constants as an aid to assigning the observed µLCR signals. Computational methods were benchmarked against previously published experimental data for (13)C60Mu in solution. Analysis of the µLCR spectrum resulted in the first experimental determination of (13)C hyperfine constants in either C70Mu or C70H. The large number of values confirms predictions that the four radical isomers have extended distributions of unpaired electron spin.

Silicon meets cyclotron: muon spin resonance of organosilicon radicals.

Muons, generated at a high-powered cyclotron, can capture electrons to form muonium atoms. Muon spin resonance spectra can be recorded for organosilyl radicals obtained by addition of muonium atoms to silylenes and silenes. We present a brief summary of progress in this new area since the first such experiments were reported in 2008.

Organic free radicals in clathrate hydrates investigated by muon spin spectroscopy.

Very little is known about the behavior of free H atoms and small organic radicals inside clathrate hydrate structures despite the relevance of such species to combustion of hydrocarbon hydrates. Muonium is an H atom analog, essentially a light isotope of hydrogen, and can be used to probe the chemistry of H atoms and transient free radicals. We demonstrate the first application of muon spin spectroscopy to characterize radicals in clathrate hydrates. Atomic muonium was detected in hydrates of cyclopentane and tetrahydrofuran, and muoniated free radicals were detected in the hydrates of cyclopentene and 2,5-dihydrofuran, indicating rapid addition of muonium to the organic guest. Muon avoided level-crossing spectra of the radicals in hydrates are markedly different to those of the same radicals in pure organic liquids at the same temperature, and this can be explained by limited mobility of the enclathrated radicals, leading to anisotropy in the hyperfine interactions.

Organosilicon compounds meet subatomic physics: Muon spin resonance.

Silylenes, germylenes and silenes react with muonium atoms, produced from muons generated at a particle accelerator. The resulting radicals can be studied by muon spin resonance spectroscopy, providing unique information about their structure and reactivity.

A silyl radical formed by muonium addition to a silylene.

Muonraker: irradiation of the stable silylene N,N'-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene with muons produced a radical that was identified as the monomeric muonium adduct from its muon spin rotation (µSR) spectrum. The muon hyperfine constant for this radical is 931 MHz, the largest ever recorded for a free radical.

Hyperfine coupling in methyl radical isotopomers.

The hyperfine coupling constants (hfcs) of two methyl radical isotopomers, CH2Mu and CD2Mu, have been measured over a wide range of temperature in ketene and ketene-d2, from which the radicals were generated. The magnitudes of the hfcs of these muoniated methyl radical isotopomers are larger than those of CH3 and CD3 due to larger zero-point energy in the out-of-plane bending mode. In contrast to CH3 and CD3, where the coupling constants become smaller with increasing temperature, the negative hfcs of the muoniated radicals were found to increase in magnitude (become more negative) with temperature, passing through a maximum near the boiling point of ketene. This behavior is attributed to a solvent-induced change in the force constant of the out-of-plane bending mode. The opposite temperature effect known for CH3 and CD3 is explained by excitation of the low frequency out-of-plane bending mode. This effect is much smaller in the muoniated radicals, where the vibrational frequency is significantly higher due to the light mass of muonium; consequently, the solvent effect dominates at low temperatures.

Organic free radicals in superheated water studied by muon spin spectroscopy.

There is a pressing need to identify and monitor reaction intermediates in water at high temperatures and pressures, but conventional techniques have limited capability for studying transient free radicals under such challenging conditions. Apparatus has now been developed to permit muon avoided-level crossing spectroscopy (muLCR) of organic free radicals in superheated water. The combination of muLCR with transverse-field muon spin rotation (TF-muSR) provides the means to identify and characterize free radicals via their nuclear hyperfine coupling constants. Because the radicals are derived from the addition of muonium (Mu = mu+ e-) to unsaturated compounds, the ensuing muoniated free radicals correspond to conventional organic free radicals but with a muon spin label substituted for one of the protons. Muon spin spectroscopy is the only technique presently being used to characterize transient free radicals under hydrothermal conditions in an unambiguous manner, free from interference from other reaction intermediates. This paper demonstrates how muoniated radicals can be used to monitor the species present in hydrothermal systems, and examples are presented from two classes of reaction: dehydration of alcohols and enolization of ketones. Spectra are displayed and hyperfine constants reported for muoniated forms of the following free radicals in superheated water (typically 350 degrees C at 250 bar): 2-propyl, 2-methyl-2-propyl (tert-butyl), and 2-hydroxy-2-propyl. The latter radical is the product of muonium addition to both the keto and the enol forms of acetone, but different isotopomers are produced according to which reaction channel is dominant. This should prove invaluable in future studies of the role of enols in combustion.

A computational study of the reactions of a beta-diketiminatoaluminium(I) complex with the hydrogen atom and the electron.

A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct.

The reactions of imidazol-2-ylidenes with the hydrogen atom: a theoretical study and experimental confirmation with muonium.

The possible radicals resulting from hydrogen atom addition to the imidazole rings of 1,3-bis(isopropyl)-4,5-dimethylimidazol-2-ylidene (1) and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (2) have been studied by means of density functional calculations (B3LYP). The calculations included solvent effects estimated via the polarized continuum model (PCM) and an empirical treatment of vibrational averaging of hyperfine constants. Addition of a hydrogen (or muonium) atom to the carbeneic carbon of 1,3-bis(isopropyl)-4,5-dimethylimidazol-2-ylidene was found to give a radical 60.46 kJ mol(-)(1) more stable than the radical resulting from addition to the double bond. Estimation of the activation barriers for reaction at the two sites shows that addition at the carbeneic carbon is favored. The site of addition was confirmed experimentally using muonium (Mu), which can be considered a light isotope of hydrogen. Muon spin rotation and muon level-crossing spectroscopy were used to determine muon, (13)C, and (14)N hyperfine coupling constants (hfc's) for the radical products of addition to the two carbenes. Good agreement between the experimental and calculated hfc's confirms that Mu (and hence H) adds exclusively to the carbeneic carbon. The radicals that are produced have nonplanar radical centers with most of the unpaired electron spin density localized on the alpha-carbon.

Enolization of acetone in superheated water detected via radical formation.

Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied.