Proton Magnetic Resonance Spectra of Aromatic and Aliphatic Thiols<sup>1</sup>

Marcus, Sheldon H.; Miller, Sidney I.

doi:10.1021/j100784a021

Cited by 31 publications

(4 citation statements)

References 4 publications

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“…Our IR spectrum of p-SWNTs displays a broad C−H stretch at 3400 cm -1 and an aromatic stretch at 1600 cm -1 ; conversion to 1 introduced a new C−Cl stretch at 1093 cm -1 , which appears as a significantly enlarged band in that region, compared to that of the p-SWNT (Figure A and B). The IR of 1 is similar to those of other aryl-SWNTs functionalized in the para position. , The difference in the C−Cl stretch frequencies for 1 versus the reactant p -chloroaniline (1095 cm -1 ) 63b is Δν = −2 cm -1 , which is similar in magnitude to those calculated for aryl-SWNTs reported by Tour, et al The IR for 1 also resembles those for model compounds Cl−Ph−R; IR frequencies for C−Cl stretches in Cl−Ph−R with R = SWNT, Ph, Me, and H are 1093, 1100, 1083, and 1091 cm -1 , respectively (Table ) . Hoping to identify an optimal model for SWNT, we also compared the characteristic frequencies that Tour reported for his other functionalized SWNTs versus their model compounds (Table ): 2954 cm -1 for t -Bu−Ph−SWNT (CH stretch), 1722 cm -1 for MeOCO−Ph−SWNT (CO stretch), and 1516 and 1339 cm -1 for NO 2 −Ph−SWNT (NO 2 ).…”

Section: Resultssupporting

confidence: 80%

“…The COSY spectrum of 1 (Figure ) reveals that the two aromatic signals are coupled and 0.18 ppm apart. This shift difference is comparable to those of 4-chlorobiphenyl (signals at 7.49 and 7.38 ppm),63a of t -butyl-4-chlorobenzene (signals at 7.31 and 7.25 ppm),63d and of 4-chlorotoluene (signals at 7.14 and 7.01 ppm),63b (Table ), which are 0.11, 0.06, and 0.13 ppm, respectively. Relative to the aromatic peaks in 4-chloroaniline (6.99 and 6.46 ppm or 7.04 and 6.54 ppm 63b ), aromatic peaks for 1 and its comparators above are farther downfield and closer together.…”

Section: Resultssupporting

confidence: 61%

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Characterizing Covalently Sidewall-Functionalized SWNTs

2007

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Pristine single-walled carbon nanotubes (p-SWNTs) were converted to 4-chlorophenyl-SWNTs 1 via treatment with 4-chlorophenylamine and isoamylnitrite, and subsequently to 4-mercaptophenyl-SWNTs 2 by using sodium ethanethiolate. Products 1 and 2 were characterized by Raman, UV/vis/NIR, TGA, IR, and 1H NMR. We report a COSY 1H NMR of 1, which appears to be the first such spectrum reported for a covalently sidewall-functionalized SWNT.

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Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 61%

Characterizing Covalently Sidewall-Functionalized SWNTs

2007

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“…This led the way to more sophisticated theories of adiabatic reaction processes [5][6][7][8], all of which converged in rate expressions similar to Eyring's. Ross and Mazur [9], as well as Pyun and Ross [lo], wrote the reactive flux in terms of reactive cross sections showing that the rate of a bimolecular reaction can be obtained as an Eyring term plus nonadiabatic and non-equilibrium corrections.…”

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confidence: 99%

Later developments of eyring's ideas of the activated complex

Hofacker

2009

Int. J. Quantum Chem.

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The clearest and most practicable ideas how to reduce the complicated problem of mechanics and statistical mechanics of a reaction complex were developed by Henry Eyring [I, 21. His theory of absolute reaction rates, the theoretical basis of untold numbers of experimental investigations, was an ingenious way of calculating approximate ensemble averages of reactive fluxes. The Eyring approach to reactive processes, as it developed from Pelzer and Wigner's phase space arguments [3] for the 3-atom case, may be characterized by the following 3 points.( I ) Neglect of Coriolis forces (for practical purposes also centrifugal forces, though these could be handled within the framework of Eyring's theory).(2) Invoking equilibrium assumptions for various degrees of freedom, e.g. the vibrations perpendicular to the reaction path.( 3 ) Simplifying the mechanical trajectories which represent reactive processes, resp. the scattering events of ingoing reactant waves, e.g. by postulating that all trajectories can cross a certain surface perpendicular to the reaction path just once or assuming that adiabatic waves (adiabatic in the sense of a Born-Oppenheimer type separation between motion along and perpendicular to the reaction path) are not scattered (See Bibliography [4]).Criticism of the activated complex model comes from the side of theory, rather than experiment. Even though it is difficult to detect rate processes which do not fit into the framework of this simple model under the disguise of thermal averages, as prevalent in most experiments, one should like to understand the implications of assumptions ( I ) to (3) on the basis of a more elaborate and functional model.There it turns out that removing Eyring's simplifications requires a great deal more of formal apparatus than one anticipated.A crude quantum mechanical derivation of transition state formulas, based on the adiabatic hypothesis stated under ( 3 ) , was given in Eyring, Walter and Kimball's book [4]. This led the way to more sophisticated theories of adiabatic reaction processes [5-8], all of which converged in rate expressions similar to Eyring's. Ross and Mazur [9], as well as Pyun and Ross [lo], wrote the reactive flux in terms of reactive cross sections showing that the rate of a bimolecular reaction can be obtained as an Eyring term plus nonadiabatic and non-equilibrium corrections. A similar result can be derived from Yamamoto's paper [l 11. An 33

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“…If this is reflected in the behavior of a solute-solvent pair, it is shown even more forcibly for different solutes in several solvents. Since 1960, five solvent contributions to 50bBd, have been postulated and discussed, bulk 5"bsd =" 5b + 5W + 5a + 5e + 5S' (2) susceptibility (5b), dispersion (5W), anisotropy (5a), electric field (5e), and specific interactions (5s1, 5S2, etc.). Despite numerous attacks (we cite only a few) on the problem of identifying and assessing the component terms of eq 2, success has been limited at best.9-14 It is of some interest therefore that regularities in the solvent effects on 5 do turn up occasionally, e.g,, in the form of eq 1. Table I There have been several reports of solute-solute relations.…”

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confidence: 99%